Nitrification inhibitors to improve fertilizer efficiency

ABSTRACT

Disclosed are compositions and methods of making a liquid fertilizer additive of biodegradable polymeric and/or oligomeric nitrification inhibitors comprised of utilizing a non-aqueous polar, aprotic organo liquid (NAPAOL) as the reaction medium for the reaction of aldehyde(s) with cyano-containing nitrification inhibitors that have one or more aldehyde reactive groups selected from the group consisting of a) primary amines, b) secondary amines, c) amides, d) thiols, e) hydroxyls and f) phenols.

The present invention claims priority under 35 USC 120 and is acontinuation in part of U.S. application Ser. No. 15/985,656 filed May21, 2018, which is a continuation in part of U.S. application Ser. No.15/967,575 filed Apr. 30, 2018, which is a continuation in part of U.S.application Ser. No. 15/854,319 filed Dec. 26, 2017, which in turnclaims priority under 35 USC 120 to U.S. application Ser. No. 15/641,264filed Jul. 4, 2017, which in turn claims priority under 35 USC 119 toU.S. Provisional Application No. 62/358,116 filed Jul. 4, 2016, theentire contents of all of which are incorporated by reference in theirentireties.

FIELD OF THE INVENTION

In embodiments, the present invention relates to liquid formulationscomprising nitrification inhibitors chemically bound within apolymer/oligomer, dispersed within a Non-aqueous Organic SolventDelivery System (abbreviated as NOSDS) for application to nitrogensources. The method of making these polymeric and/or oligomericnitrification inhibitors comprise a non-aqueous polar, aprotic organoliquid (abbreviated as NAPAOL) that is utilized as the reaction mediumfor the reaction of aldehyde(s) with cyano-containing nitrificationinhibitors that have one or more aldehyde reactive groups selected fromthe group consisting of a) primary amines, b) secondary amines, c)amides, d) thiols, e) hydroxyls and f) phenols and wherein the processparameters are optimized for conserving the cyano group. A non-aqueoussolvent delivery system (NOSDS) can be utilized to improve the physicalproperties of the liquid formulation wherein the NOSDS comprises thereaction medium, NAPAOL, aprotic solvents and protic solvents which areenvironmentally friendly, have flashpoints above 145° F. and areinherently rated safe for contact with humans and animals.

In embodiments, the present invention relates to liquid formulationscontaining hydrophobic, biodegradable polymers dispersed within aNon-aqueous Organic Solvent Delivery System (NOSDS) and is designed tocoat fertilizer granules with a hydrophobic film utilizing simpleapplication equipment such as mixers, blenders and tumblers. This filmcan impede the dissolution of fertilizer components by water improvingfertilizer efficiency. The NOSDS can be aprotic solvents, proticsolvents and mixtures of protic and aprotic solvents which areenvironmentally friendly, have flashpoints above 145° F., and areinherently rated safe for contact with humans and animals. Thehydrophobic polymers are the reaction product of aldehyde(s) andnitrogen containing compounds.

BACKGROUND OF THE INVENTION

Fertilizer efficiency has become a major issue in the world. The majorelement of fertilizer is nitrogen (N). In one study, using data fromover 800 experiments, it was estimated that only 51% of the N appliedwas recovered by cereals plant (Dobermann and Cassman 2005). In anotherstudy, it was reported that average N recovery in cereals in China was30-35% (Fan 2004). Phosphorous is the second largest element infertilizer compositions and its efficiency is even lower. It wasestimated to be around 10-25% (Unsay 1979). Potassium is the thirdlargest fertilizer composition and its efficiency is around 40% (BaligarV C 1986).

One of the main factors for the low efficiency of fertilizers is due tothe excellent water solubility of many of its components. In practice,fertilizers are often just applied once at the beginning of the growingseason. After the application, nutrients from fertilizers are dissolvedin water and released to soil in amounts that are too much for plants toabsorb. The unabsorbed nutrients can be leached to the environment, andfind their way to surface water such as ponds, lakes and rivers orcontinue to leach into the sub-surface water table contaminating many ofthe rural community water supplies. Low efficiency of fertilizer notonly increases the cost of fertilization, but also contributessignificantly to environmental pollution. In the case of nitrogen basedfertilizers, one of the major mechanisms for its poor efficiency is theimpact of biologically driven processes on water solubilized sources ofnitrogen. Urea is the main component of most nitrogen fertilizers. Inthe presence of soil moisture, natural or synthetic ureas are dissolvedand are converted to ammonium ion by bacterial activity, making thenitrogen available for plant uptake. Ammonium can be further convertedby bacteria in soil to nitrate through a process called nitrification.Nitrate is also available for plant uptake. Excess ammonia not absorbedby plants can leach into water which can be toxic to water creatures (USEPA822-R-13-001). Excess nitrates can also leach into water, causing theincreasing of nitrate concentration in the ground water. Consumption ofnitrate contaminated water by human can cause methemoglobinemia (bluebaby syndrome) (Kross, Hallberg et al. 1993). Moreover, excessivenitrate can be converted into nitric oxide or nitrous oxide by certaintypes of bacteria in the soil, through a biological process calleddenitrification. Nitrous oxide is a potent greenhouse gas, whose potencyon global warming is 300 times stronger than carbon dioxide(http://epa.gov/climatechange/ghgemissions/gases/n2o.html). In the caseof phosphate fertilizer, phosphate fertilizer in the soil can be erodedinto the river causing eutrophication, which can pose severe damage tothe whole water body (Bennett EM 2001). Over usage of potassiumfertilizer has been associated with deterioration of soil structure, Theother problem associated with the over usage of potassium fertilizer isthe disruption of the balance of nutrients in the soil such as Ca, Feand Zn, that are in a plant available form (S 2012).

The goal of the worldwide agricultural industry is to increase theefficiency and decrease the environmental impact of fertilizer. Onemethod is to apply the fertilizer in small doses but with morefrequency. However, this approach will incur increased labor cost and isnot economically practical, especially in developed countries, where thelabor cost tends to be higher. A preferred method is to slow down thedissolution of water soluble fertilizer components and extend the periodof time for release of nutrients in a plant available form. The currenttechnological trend for slowing dissolution of fertilizer is focused oninventions that utilize various types of coatings which control water'saccess to the fertilizer's water soluble components. While manyinventions claim the ability to coat any of the fertilizer components,the major commercialized coating-based products are centered aroundurea. To implement these inventions usually require separate processsteps, heat and specialized application equipment for application ofcoatings to fertilizer. The choice of coating urea is based on (1) Ureais usually produced through a synthetic process making the additionalsteps of coating conveniently part of the overall urea preparationprocess, (2) urea is one of the more costly as well as one of thelargest components in a fertilizer formulation and (3) urea bonds wellwith most organic coatings versus the inorganic nature of the othercomponents of fertilizer. The core of the technology is that coatingurea prills (granules) with a water-insoluble, semipermeable, orimpermeable (with pores) material delays the release of N from the urea.Urea is highly soluble in water, but the solubility of coated urea isdependent on the coating material, its thickness, and the coverage anduniformity of the coating on the granule.

The first widely used urea coating technology is a sulfur coating inU.S. Pat. No. 3,342,577 (Blauin) which demonstrates a process of sulfurcoating of urea particles to slow dissolution. It was developed in thelate 1960's by the Tennessee Valley Authority (TVA) as an economicalsystem for reducing the rate of dissolution when urea particles areapplied to the soil as fertilizer. The release of nutrients fromsulfur-coated fertilizers occurs by diffusion of water throughimperfections in the sulfur coating and through coating breakdown. Inthis technology, urea is coated with molten sulfur. It is sometimestopped with a coating of wax to overcome the numerous granule surfaceimperfections as well as to mitigate damage to the coating throughprocessing, packaging, storage and transport of the coated urea. Sulfuris water impermeable, but the cracks on the surface allow water topenetrate in the beginning. Overtime, sulfur is degraded by bacteria inthe soil and urea is totally released (Christians 2004).

U.S. Pat. No.4,551,166—(Behnke) discloses that the addition ofdicyandiamide (DCD) can be carried out at several points in theurea-formaldehyde condensation reaction and utilize water as thereaction medium. DCD can either be added right at the beginning of thereaction, together with the urea and the formalin, or later during thereaction or at the end of the reaction, before or after cooling. Benkealso discloses that the methylene bisurea analogue, methylenebisdicyandiamide, is not formed during the reaction.

Attempts to seal the sulfur coating have been described in U.S. Pat. No.5,219,465 (Goertz), by utilizing a polymethylenepoly(phenyl-isocyanate), a catalyst to promote polyurethane curing withpolyester polyols to topcoat the sulfur on the surface.

U.S. Pat. No. 5,599,374 (Detrick) relates to a process for producingsulfur-coated, slow release fertilizers having a uniform, durablepolymeric coating over the sulfur-coating which improves impact andabrasion resistance properties. This polymer coating is formed by thedirect in situ co-polymerization of diethylene glycol-triethanolaminepolyol and a diisocyanate on the surface of the sulfur-coated ureagranule.

U.S. Pat. No. 5,653,782 (Stern et. al.) describes a process by whichfertilizer particles are preheated to a temperature in excess of themelting point of sulfur (115° C.), prior to being mixed with solidsulfur prills. The resulting fertilizer is comprised of fertilizerparticles contained in a sulfur matrix.

U.S. Pat. No. 6,338,746 (Detrick et al.) describes a process of firstcoating a fertilizer with a polymer, then coating the polymer withsulfur and thereafter applying a polymer coating.

U.S. Pat. Application, 20100011825 (Ogle, et al.) teaches that multiplelayers of coating for urea granules in which the urea is coated with apolymeric layer, an intermediate layer and sulfur layer outside.

While sulfur represents a low cost coating, it still required separatemanufacturing steps, high temperatures (>120 C) and is not attritionresistant during processing, packaging, storage and transporting withoutthe addition of other additives. Urethane polymer technologies have alsobeen developed to coat urea fertilizer, which allows more precise rateof nitrogen release than sulfur coated urea. U.S. Pat. No. 3,264,089(Hansen) and U.S. Pat. No. 3,475,154 (Kato) inventions involve preformedpolymers in quick drying solvents. As these solvents are flashed off,their fumes create a low flash point hazard and can result in pinholeimperfections on the coated fertilizer. Isocyanate based polymers areutilized in a number of inventions which are based on a plurality ofcoatings in which a urethane polymer is formed on the surface of afertilizer particle through separate coating of an isocyanate capable ofcrosslinking with compounds having multiple active hydrogens such aspolyols or polyamine. Most inventions also include a final coating thatis hard but not brittle to improve resistance to damage to the coatingsduring processing, packaging, storage and transport.

U.S. Pat. No. 5,538,531 (Hudson et al.) describes controlled releasefertilizers and a method for their production. These controlled releasefertilizers have a central mass of particulate fertilizer which containsat least one water soluble plant nutrient surrounded by a plurality ofcoatings. The inner coating comprises the reaction product of anaromatic, a polyol having from 2 to 6 hydroxyl units and at least onealkyl moiety containing from about 10 to 22 carbon atoms. An outercoating of a wax is also necessary.

U.S. Pat. No. 5,803,946 (Petcavich, et al.), teaches a urea particulateplant nutrient having on its surface an interpenetrating polymer networkcomprising a biuret, a urethane and tong oil.

U.S. Pat. No. 6,663,686 (Geiger et al.) teaches a process in which waxis used as a component of the polyurethane coating, not as a separateover-coat. The invention describes controlled release can be achievedwith less coating materials and by a relatively simple procedure whichin turn, permits the reduction of coat thickness.

U.S. Pat. Application, 20040016276 (Wynnyk, et al.), utilizes anisocyanate and castor oil to build a urethane polymer for controlrelease of the water soluble components of fertilizer and incorporatesan inorganic and/or an organic particulate filler and, optionally, a waxin a one-step coating process. The addition of the particulate filler istouted as improving processing, handling, packaging and transport.

While many of these inventions have been shown to slow down thedissolution of urea, the processes, equipment and chemistries result ina coated urea that is very expensive when compared to uncoated urea andis mainly used for expensive crops and turf industry (LAL 1998). Many ofthese coatings also provide no nutritional value for plants.

Although the listed inventions claim to provide a coating to limitdissolution of other fertilizers components such as phosphorus,potassium and micronutrients, the cost of the application of suchtechnologies has impaired their entry into the agricultural marketplace.While many of the coating technologies have strategies to overcome theattrition of coverage of the urea particle, the inorganic nature of theother fertilizer components causes difficulties in the adhesion of thecoatings to the inorganic particles. Natural based fertilizers such asmanure are also not coated due to the cost of the coating operations,the quick loss of nitrogen value due to existing bacteria population andmanure's amorphous physical nature.

Patent CN104803807 (Yuan) teaches us that urea, ammonium phosphate,potassium chloride, diammonium phosphate, monoammonium phosphate,potassium nitrate, potassium dihydrogen phosphate, magnesium humate,zinc humate, urea ion humate or nitro humic acid granules can be coatedwith dicyclopentadiene, glycerol ester copolymer, polyvinyl alc., andPMSM (p-methylstryrene-maleic anhydride copolymer).

Patent CN 104609983(Li, et al.) teaches us that a hydrophobic film isformed on the surface of fertilizer granules by in situ reaction ofpolymethylene polyphenyl polyisocyanate and polyether polyol.

Patent CN 104446875 (Chen, et al.) teaches us that polycondensationreaction of citric acid, polyglycolic acid and potassium carbonate canform a slow releasing potassium fertilizer.

While all these technologies can slow down the dissolution of watersoluble inorganic fertilizer components, the cost of the specializedequipment, chemistries and processing to produce the coated particle andthe attrition of the coating coverage during processing, packaging,storage and transport has severely limited their utility foragriculture. Moreover, all these fertilizer must be made according tocertain specifications in large volume and cannot be tailored tocustomer's specific needs. In light of the above, it is desirable todevelop a slow release fertilizer coating technology which isenvironmental-friendly, low cost and can be applied with simpleapplication equipment such as mixers blenders or tumblers. Moreover,this technology should be flexible enough to prepare small batchesaccording to the customer's needs.

U.S. Pat. No. 9,440,890 (Gabrielson) teaches reaction products may beformed from the reaction of formaldehyde, DCD, urea, and an ammoniasource in water which may be included in agricultural products,including fertilizer compositions and nitrification inhibitor systems.Gabrielson also states that fertilizer compositions that include thereaction product can be beneficial for reducing leaching ofnitrification inhibitors applied to soil. However, the reactions areperformed in an aqueous medium which limits their applications tosystems or processes not negatively impacted by the presence of water.Gabrielson's invention also requires other formaldehyde reactiveconstituents such as urea and ammonia which have excellent watersolubility to assist with the dissolution of dicyandiamide (DCD) sinceDCD has a limited solubility in water of approximately 32 grams/liter at20° C. resulting in slower reactivity and low concentrations of DCDincorporated into the resulting polymers and/or oligomers. The resultingcomposition of the reaction product is reported to be a mixture of atriazonyl-formaldehyde-DCD adduct, a urea-formaldehyde-DCD adduct, and aDCD-formaldehyde-oligomer adduct.

In fact, the reported composition of the formaldehyde reaction productcomprises only about 0.1 to 10 wt. % of a DCD-formaldehyde-oligomeradduct based upon the weight of the nitrification inhibitor system.Since the described invention requires water as a reaction medium anddue to research reports that the presence of water is essential indriving the degradation of dicyandiamide to diaminomethylene ureas asshown in the following reaction,

the loss of the cyano-group would diminish the product's nitrificationinhibition capabilities either directly or in a slow release mechanismthat is dependent on microbial activity to break down thepolymer/oligomer releasing dicyandiamide over time.

Gabrielson presents analytical data in Table 7 that utilizes the ionizedmass results from a LCMS (liquid chromatograph mass spec) examination ofexample 2 to derive a few structures of example 2's composition. Example2 is the reaction products of ammonia, dicyandiamide and urea withformaldehyde, wherein the reaction medium is water. Below in Table 1 isa complete listing of the potential structures for the remaining ionizedmass results that were not identified:

TABLE 1 LCMS Spectral Peak Identification Ionized Mass + Peak # Na (23Da) Proposed Structure  1 148

 2 DCD  3 Urea  4 220

 5 Unknown/Appears in Nitamin 30L  6 Unknown/Appears in Nitamin 30L  7179

 8 251.1

 9 261.1

10 244.1

11 155.0 Unknown/Appears in Nitamin 30L

12 220

13 292.1

14 220

15 196.0 Unknown/Appears in Nitamin 30L

Upon examination, the data lacks the ionized mass results for methylenebis dicyandiamide (180+23 (Na)=203) and the dicyandiamide-formaldehydetrimer (276+23(Na)=299). It also shows the presence of unreacted DCD.Garbrielson discloses a composition of the formaldehyde reaction productcomprises 0.1 to 10 wt. % of a DCD-formaldehyde-oligomer adduct basedupon the weight of the nitrification inhibitor system but the analyticaldata does not indicate the compound to be present.

Gabrielson tests the performance of his innovations as nitrificationinhibitors wherein the application levels with urea are based on the DCDcontent of his examples 1-3. Table 2 show the weight of DCD required foreach experiment. Table 2 also translates the weight of DCD utilized inthe evaluation into pounds DCD/ton of urea (Standard terminology for AgIndustry).

TABLE 2 *Level of Weight of Weight of Weight of Lbs DCD/ DCD Ureanitrogen DCD ton of urea 0.75% 2.15 0.989 0.00742 6.90 1.50% 2.15 0.9890.01484 13.80 3.00% 2.15 0.989 0.02967 27.60 *based on nitrogen contentof urea ** urea is approximately 46% nitrogen

The expected % DCD content of each example based on the given weights ineach examples including the distillation loss of Example 2 wascalculated. Table 3 shows the expected weights of each example in theperformance experiments as well as translating these weights intopounds/ton of urea (Standard terminology for the Ag Industry)

TABLE 3 0.75% DCD on N value of urea 1.5% DCD on N value 3.0% DCD on Ngrams of of urea value of urea Expected Example Lbs of grams of Lbs ofgrams of Lbs of % DCD in 500 Example/ Example Example/ Example Example/Example (Bound ml ton of in 500 ml ton of in 500 ml ton of # and free)solution urea solution urea solution urea 1 38.36% 0.0193 17.987 0.03935.97 0.077 71.95 2  7.98% 0.0930 86.466 0.186 172.93 0.372 345.86 318.58% 0.0399 37.137 0.080 74.27 0.160 148.55

The resulting evaluation on the effectiveness of the nitrificationinhibition by the experimental samples showed that example 2 was moreeffective versus examples 1 and 3 and example #2 was equivalent to C2(DCD & Urea) but only at the application level of 3% DCD based on thenitrogen content of urea. Example 2 performed poorer versus DCD at lowerlevels.

Earlier work in U.S. Non-Provisional application Ser. No. 15/641,264(McKnight) filed Jul. 4, 2017 (to which the present invention claimspriority) discussed the use of an aprotic non-aqueous ogano solventdelivery system NOSDS comprising one or more aprotic solvents that canserve as the reaction medium for the formation of biodegradable,hydrophobic polymers that are the reaction product of aldehyde(s) andnitrogen containing compounds. McKnight also detailed a process whereinsaid biodegradable, hydrophobic polymer involves 1) dissolving thenitrogen containing compound into an aprotic NOSDS at temperatures of10-140° C. wherein the composition is cooled to 30-60° C. 2) thealdehydes are charged at a rate that controls the exotherm with 5-20° C.of the reaction temperature that is 30-90° C. in a molar ratio ofaldehyde to aldehyde reactive sites on the nitrogen containing compoundof (0.10-0.90)/1.0. 3) The reaction is held at 30-70° C. and at a pH of7.5-10.0 for 5 to 12 hours until the free formaldehyde is 40,000 to5,000ppm's. 4) The reaction is heated to 70-100° C., the pH is adjustedto 4.0-8.0 and held until free formaldehyde is <700 ppm, wherein thecomposition is cooled to less than 40° C. and packaged. McKnight alsostated that the resulting biodegradable, hydrophobic polymer dispersedwithin the aprotic NOSDS imparted good water resistant properties tourea. However, it has been determined that the reaction conditions toproduce these biodegradable polymers/oligomers were too aggressive forcyano-containing nitrification inhibitors resulting in the conversion ofthe cyano-group to a carbamide function impacting solubility and mostimportantly, nitrification inhibition. Also McKnight demonstratedurea-formaldehyde reactions utilizing dimethyl sulfoxide as the reactionmedium in Examples 17 and 18.

Thus, there is a need to for compositions and an improved method ofmaking liquid fertilizer additives of biodegradable polymers and/oroligomers comprised of the reaction products of aldehyde(s) withcyano-containing nitrification inhibitors that have one or more aldehydereactive groups.

Although the concept of creating a larger molecular weight nitrificationinhibitor would assist in slowing its migration through the soil, theindustry needs a product that is economical, effective at lowerapplication levels and utilizes a liquid delivery system that isnon-aqueous in order to be utilized in all nitrogen source applicationtechniques. It would also be beneficial to have a method to make amodified urea in situ during the urea manufacturing/particle formationprocesses wherein a liquid fertilizer additive comprising partiallyreacted/unreacted nitrification inhibitors—aldehyde compositions isadded to the molten urea utilizing a non-aqueous polar, aprotic solventsystem. Moreover it is beneficial to have urea and ammonia have goodsolubility in the delivery vehicle. In a variation, the liquidfertilizer additive is added to anhydrous ammonia, a molten pool of ureaand/or a molten pool of urea that is either in an ammonia atmosphere,has ammonia dissolved within the molten pool or that has ammonia addedduring the charge of the liquid fertilizer additive.

SUMMARY OF THE INVENTION

In embodiments, the present invention relates to liquid formulationscontaining hydrophobic, biodegradable polymers dispersed within aNon-aqueous Organic Solvent Delivery System (NOSDS) and is designed tocoat fertilizer granules with a hydrophobic film utilizing simpleapplication equipment such as mixers, blenders and tumblers. This filmcan impede the dissolution of fertilizer components by water improvingfertilizer efficiency. The NOSDS can be aprotic solvents, proticsolvents and mixtures of protic and aprotic solvents which areenvironmentally friendly, have flashpoints above 145° F., and areinherently rated safe for contact with humans and animals. Thehydrophobic polymers are the reaction product of aldehyde(s) andnitrogen containing compounds.

In an embodiment, the present invention relates to compositions and animproved method of making liquid fertilizer additives of biodegradablepolymers and/or oligomers comprised of the reaction products ofaldehyde(s) with cyano-containing nitrification inhibitors that have oneor more aldehyde reactive groups selected from the group consisting ofa) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols, wherein the cyano-group is conserved.

The present invention also relates to a method of making non-aqueousliquid fertilizer additives that are comprised of high levels ofbiodegradable polymers and/or oligomers, especially methylene busnitrification inhibitor (NI) oligomers as shown below:

(2 moles) NI+(1 mole) formaldehyde unit→NI—CH₂—NI+H₂O

wherein the reaction of aldehyde(s) with non-cyano-and/orcyano-containing nitrification inhibitors that have one or more aldehydereactive groups selected from the group consisting of a) primary amines,b)secondary amines, c) amides, d) thiols, e) hydroxyls and f) phenolsutilizing a non-aqueous polar, aprotic organo liquid (abbreviated asNAPAOL) as the reaction medium to produce compounds overcomingperformance deficiencies related to atmospheric volatility or migrationthrough the soil due to water solubility and low molecular weight. It isthought that these methylene bis NIs as well as polymeric NIs havenitrification inhibition properties as well as providing nitrificationinhibition through a slow release mechanism of biodegradation of theoligomer and/or polymer that releases the polymer bound nitrificationinhibitor. The utility of a NAPAOL as the reaction medium allowsaldehyde reactions with non-cyano-containing nitrification inhibitorsthat have been previously unavailable due to the poor water solubilityof the non-cyano-containing nitrification inhibitors.

The capability of the NAPAOL to also serve as a non-aqueous organosolvent delivery system (abbreviated as NOSDS) allows the application ofthe liquid composition to nitrogen sources that utilize moisturesensitive application methods. It has been learned that liquidfertilizer additives of biodegradable polymers and/or oligomerscomprised of utilizing a non-aqueous polar, aprotic organo liquid(NAPAOL) as the reaction medium for the reaction of aldehyde(s) withcyano-containing nitrification inhibitors that have one or more aldehydereactive groups selected from the group consisting of a) primary andsecondary amines, b) amides, c) thiols, d) hydroxyls and e) phenolsassist to conserve the cyano-group. It has also unexpectedly learnedthat the liquid fertilizer additives of biodegradable polymers and/oroligomers comprised of utilizing a non-aqueous polar, aprotic organoliquid (NAPAOL) as the reaction medium for the reaction of aldehyde(s)with nitrification inhibitors that have one or more aldehyde reactivegroups selected from the group consisting of a) primary and secondaryamines, b) amides, c) thiols, d) hydroxyls and e) phenols, wherein theresulting product can possesses higher levels of polymer bound and freenitrification inhibitors versus products utilizing a NAPAOL to makesolutions of free nitrification inhibitors. In a variation, it has beenlearned that utilizing a NAPAOL as the reaction medium results in highercompositional weight percent of said biodegradable polymers and/oroligomers versus those produced in an aqueous medium.

In embodiments, the present invention relates to liquid formulationscomprising nitrification inhibitors chemically bound within apolymer/oligomer, dispersed within a Non-aqueous Organic SolventDelivery System (abbreviated as NOSDS) for application to nitrogensources. The method of making these polymeric and/or oligomericnitrification inhibitors comprise a non-aqueous polar, aprotic organoliquid (abbreviated as NAPAOL) that is utilized as the reaction mediumfor the reaction of aldehyde(s) with cyano-containing nitrificationinhibitors that have one or more aldehyde reactive groups selected fromthe group consisting of a) primary amines, b) secondary amines, c)amides, d) thiols, e) hydroxyls and f) phenols and wherein the processparameters are optimized for conserving the cyano group. A non-aqueoussolvent delivery system (NOSDS) can be utilized to improve the physicalproperties of the liquid formulation wherein the NOSDS comprises thereaction medium, NAPAOL, aprotic solvents and protic solvents which areenvironmentally friendly, have flashpoints above 145° F. and areinherently rated safe for contact with humans and animals.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is the plot of DCD concentration in samples of the presentinvention versus UV absorbance @ 211-216 nm.

FIG. 2 is an FTIR scan of Example 76.

FIG. 3 is an FTIR scan of Example 74.

FIG. 4 is an FTIR scan of Example 79

FIG. 5 is an FTIR scan of a 34% solution of Dicyandiamide in DMSO

FIG. 6 is a graph of nitrification inhibition properties of Examples 73and 76 versus dicyandiamide

FIG. 7 is a graph on the impact of the presence of the cyano group onnitrification inhibition properties

FIG. 8 is the nitrification inhibition property of Example 75 versusdicyandiamide.

FIG. 9 is the chromatogram of Example 76.

FIG. 10 is the mass spectra of Example 76.

FIG. 11 is the chromatogram of Example 78.

FIG. 12 is the mass spectra of Example 78.

DETAILED DESCRIPTION OF THE INVENTION

Definitions:

cyano-containing nitrification inhibitor: nitrogen containing compoundsthat have nitrification inhibition properties and contain one or morecyano-groups.

non-cyano-containing nitrification inhibitor: nitrogen containingcompounds that have nitrification inhibition properties and contain nocyano-groups.

NAPAOL (non-aqueous polar, aprotic organo liquid): an aprotic NOSDS(non-aqueous organo solvent delivery system) that is used specificallyas the reaction medium.

biologics: although utilized as bio-active agents are specified as adifferent category due to their definition as naturally occurringsubstances, substances produced by natural processes such asfermentation and/or extracts of naturally occurring substances.

nitrogen sources: one or more compounds and/or substances selected fromthe group consisting of: urea, urea formaldehyde reaction products,ammonia, urea formaldehyde and ammonia reaction products, ammoniumnitrate, ammonium sulfate, manure and compost.

treated nitrogen source: a composition comprising a nitrogen source andbiologically active agents and/or biologics added either through acoating application or added to the nitrogen source during the nitrogensource's production process either in the melt portion or applied to thenitrogen source during the formation of the nitrogen source's granule.

Polymer weight or polymer composition weight refers to the nitrificationinhibitor weight.

In one embodiment, the present invention relates to liquid formulationscomprised of hydrophobic, biodegradable polymers and a Non-aqueousOrganic Solvent Delivery System (NOSDS) and is designed to coatfertilizer granules with a hydrophobic film utilizing simple applicationequipment such as mixers, blenders and tumblers A NOSDS is comprised ofa) one or more protic solvents from the group consisting of: 1) analcohol from the family of C₁₋₁₀ alkanols, 2) one or more polyols fromthe group consisting of trimethylol propane, trimethylol ethane,pentaerythritol, sorbitol and sorbitan, glucose, fructose, galactose,and glycerin, 3) poly(C₁₋₁₀ alkylene) glycols, 4) one or more alkyleneglycols from the group consisting of ethylene glycol, 1,3 propyleneglycol, 1,2 propylene glycol, and butylene glycol, 5) isopropylideneglycerol 6) one or more alkylene glycol alkyl ethers represented by thestructure:

-   -   where R¹ is: CH₃, C₂H₅, C₃H₇ or C₄H₉    -   where R² is: H or

-   -   where R³ is: H or CH₃    -   where R⁴ is H and/or CH₃    -   and f is an integer between 1 and 15        7) one or more alkyl lactates from the group consisting of        ethyl, propyl and butyl lactate, 8) one or more alkanolamines        represented by the structure:

-   -   where R⁵ is: C₂H₄OR⁸ or C₃H₆OH    -   where R⁶ is: H, C₂H₄OR⁸ or C₃H₆OH    -   where R⁷ is: H, C₂H₄OR⁸ or C₃H₆OH    -   where R⁸ is: (C₂H₄O)_(g)H    -   and g is an integer between 1-10        and 9) glycerol carbonate.        b) and/or one or more aprotic solvents from the group consisting        of 1) dimethyl sulfoxide and/or 2) dialkyl, diaryl, or alkylaryl        sulfoxide(s) having the formula:

R₉S(O)_(x)R₁₀

-   -   wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylene group,        an aryl group, or C₁₋₃alkylenearyl group or R₉ and R₁₀ with the        sulfur to which they are attached form a 4 to 8 membered ring        wherein R₉ and R₁₀ together are a C₁₋₆ alkylene group which        optionally contains one or more atoms selected from the group        consisting of O, S, Se, Te, N, and P in the ring and x is 1 or        2.        3) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate, 4) one or more polyols capped with acetate        or formate wherein the polyol portion selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and glycerin, 5) one or more        alkylene glycol alkyl ethers acetates selected from the group        consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and/or tripropylene        glycol butyl ether acetate and, 6) isophorone, 7) one or more        diesters consisting of dimethylsuccinate, dimethyl adipate,        diethyl glutarate, and dimethyl glutarate, 8)        dimethylacetamide, 9) dimethylformamide, 10)        dimethyl-2-imidazolidinone, 11) 1-Methyl-2-pyrrolidone, 12)        hexamethylphosphoramide, 13) 1,2-dimethyloxyethane, 14)        2-methoxyethyl ether, 15)cyclohexylpyrrolidone and 16) limonene.

In one embodiment, the biodegradable, hydrophobic polymers are thereaction product of aldehyde(s) and nitrogen containing compounds. In anembodiment, the aldehyde(s) comprising one or more of the groupconsisting of

-   -   Q is: O, S    -   Where R¹¹ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —CH═CH₂,        —C₄H₃O, —C₇H₇, —C₆H₅, —C₆H₁₁, CHO, C₂H₃O, C₃H₅O, C₄H₇O, C₇H₅O or        —R¹²O₂R¹³,    -   Where R¹² is: —C, —C₂H₂, —C₃H₄, —C₄H₆, —C₅H₈, —C₆H₁₀    -   Where R¹³ is: —H, CH₃, C₂H₃, C₃H₇, C₄H₉

In one embodiment, the nitrogen containing compounds comprising one ormore of the group consisting of

-   -   A is: O, S    -   where R¹⁴ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(a)NH₂        -   Where a is an integer: 1-10    -   where R¹⁵ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(b)NH₂        -   Where b is an integer: 1-10    -   where R¹⁶ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(c)NH₂    -   Where c is an integer: 1-10        -   where R¹⁷ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅,            —CONH₂, —(CONH)_(d)NH₂        -   Where d is an integer: 1-10            and

and their tautomeric forms and

-   Where X₁ is: —NHR¹⁸, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   Where R¹⁸ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂,    -   C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅-   Where X₂ is: —NHR¹⁹, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   Where R¹⁹ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂,    -   C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅-   Where X₃ is: —NHR²⁰, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   Where R²⁰ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂,    -   —C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅-   and-   NH₂CO—R²¹-   where R²¹ is an alkyl radical CH3 to —C17H35

In a variation, an aldehyde can be reacted with a nitrogen containingcompound to form a new monomer. A non-limiting example would be thechemical Tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione from thereaction of 2 moles of urea and one mole of ethandial and represented bythe structure:

In another variation, the monomeric reaction product of an aldehyde anda nitrogen containing compound can be capped with a C₁-C₄ alkanol groupcreating a low temperature crosslinking product.

Non-limiting examples would be 1,3,4,6-Tetrakis(methoxymethyl)glycolurilfrom the reaction of one mole ofTetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione with four moles ofmethanal and then capping with four moles of methanol.

N,N,N′,N′,N″,N″-Hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triaminefrom the reaction of one mole of 1,3,5-triazine-2,4,6-triamine with 6moles of methanal and then capping with six moles of methanol.

Tetra(methoxymethyl) urea from the reaction of 1 mole of urea with fourmole of methanal and then capped with four moles of methanol.

In one embodiment, the biodegradable, hydrophobic polymers that are thereaction product of aldehyde(s) and nitrogen containing compoundscontain polyamines such as but not limited to ethylenediamine,diethylenetriamine, triethylenetetramine tetraethylenepentamine andaminoethylethanolamine and/or polyol compounds such as but not limitedto one or more polyols from the group consisting of trimethylol propane,trimethylol ethane, pentaerythritol, sorbitol and sorbitan, glucose,fructose, galactose, and glycerin, 3) poly(C₁₋₁₀ alkylene) glycols, 4)one or more alkylene glycols from the group consisting of ethylene, 1,3propylene glycol, 1,2 propylene glycol, and butylene glycol, 5)isopropylidene glycerol 6) one or more alkylene glycol alkyl ethers fromthe group consisting of tripropylene glycol methyl ether, tripropyleneglycol butyl ether, dipropylene glycol butyl ether and tripropyleneglycol butyl ether constituting 0.1-5% of its polymer weight in order tomodify the coatings' properties such as hydrophobicity, coverage,flexibility of the formed film. The polymer weight means thenitrification inhibitor weight.

In one embodiment, the biodegradable, hydrophobic polymers that are thereaction product of aldehyde(s) and nitrogen containing compoundscontain secondary amines such as diethanolamine, diethylamine,cyclohexylamine, methylethanolamine, diisopropanolamine,methylispropylamine and small molecular weight alcohols such as but notlimited to methanol, ethanol, butanol, and hexanol to assist incontrolling the molecular weight build of the biodegradable, hydrophobicpolymer through chain termination

In one embodiment, the biodegradable, hydrophobic polymers are thereaction product of aldehyde(s) and nitrogen containing compounds inwhich the aldehyde(s) comprising one or more of the group consisting of:

-   -   methanal, ethanal, propanal, butanal, pentanal, hexanal,        methylethanal, methylpropanal, methylbutanal,        phenylacetaldehyde, benzaldehyde, 2-propenal, 3-oxopropanoic,        2-methyl-3-oxopropanoic acid, 4-oxobutanoic acid, oxoacetic        acid, 5-oxopentanoic acid, 6-oxohexanoic acid, 2-oxopropanal,        cyclohexanal, furfural    -   methyl esters of 3-oxopropanoic, 2-methyl-3-oxopropanoic acid,        4-oxobutanoic acid, oxoacetic acid, 5-oxopentanoic acid and        6-oxohexanoic acid, ethandial, 1,3-propanedial, butanedial,        pentanedial, phthalaldehyde and methanethial        and nitrogen containing compounds comprising one or more of the        group consisting of    -   urea, biuret, polyurea, thiourea, methylurea, dimethylurea,        ethylurea, diethylurea, propylurea, dipropylurea, butylurea,        dibutylurea, phenylurea, diphenyl urea, pentylurea,        dipentylurea, hexyl urea, dihexyl urea, methylthiourea,    -   dimethylthiourea, ethylthiourea, diethylthiourea,        propylthiourea, diporpylthiourea, butylthiourea,        dibutylthiourea, pentylthiourea, dipentylthiourea,        hexylthiourea, dihexylthiourea, phenylthiourea,        diphenylthiourea, cyanamide, dicyandiamide, tricyantriamide,        melamine, hydroxy oxypentyl melamine, methylaminomelamine,        dimethylaminopropylmelamine, 1,3,5-Triazine-2,4,6 triamine,        2,4-diamino-1, 3,5-triazine, 2,4-diol-6-Amino-1,3,5-triazine,        2,4-Diamino-6-hydroxy-1,3,5-triazine,        2-Butylamino-4,6-diamino-1,3,5-triazine,        2,4-Diamino-6-methyl-1,3,5-triazine,        2,4-Diamino-6-dimethylamino-1,3,5-triazine,        2-Amino-1,3,5-triazine, ethanamide, propanamide, butanamide,        pentanamide, hexanamide, heptanamide, octanamide, nonanamide,        decanamide, dodecanamide, tetradecanamide, hexadecanamide, and        octadecanamide, ammonia, monoethanolamine, diglycolamine,        ethylamine,

In one embodiment, the NOSDS of the present invention meet one or moreof the following criteria: They are:

-   environmentally safe;-   thermally safe because they have flashpoints above 145° F.;-   inherently rated safe for contact with humans and animals;-   able to maintain biodegradable, hydrophobic polymers that are the    reaction product of aldehyde(s) and nitrogen containing compounds at    levels of 1-50% in solution to temperatures down to at least 10° C.    This property means that these compositions have improved shelf    storage lives.-   able to provide improved and even application to fertilizer granules    of biodegradable, hydrophobic polymers that are the reaction product    of aldehyde(s) and nitrogen containing compounds while not causing    clumping of the granules.

In an embodiment, low molecular weight biodegradable, hydrophobicoligomers(LMWBHO) with a molecular weight range of 50-1000 daltons fromthe reaction of aldehyde(s) and nitrogen containing compounds can beproduced utilizing an aprotic NOSDS as the reaction medium. In avariation, the molar ratios of aldehyde groups to aldehyde reactivenitrogens are 0.1-1.5/0.5-1.5. In another variation, these LMWBHOs canbe blended with one or more monomeric reaction products of an aldehydeand a nitrogen containing compound that have been alkoxy capped at a %weight ratio of 99.9-90%/0.1-10% of LMWBHO/alkoxy capped monomers. Thisblend can be applied to the surface of fertilizer granules, then exposedto temperatures 25-100° C. causing crosslinking reaction to occurbetween the alkoxy capped monomers and the LMWBHO. In a variation, thoseskilled in the art can add a catalyst such as

-   -   methane sulfonic acid, sulfuric acid, para-toluene sulfonic        acid. phosphoric acid and methane phosphonic acid        to the coating formulation to improve reactivity and conversion.        In a variation, the alkoxy capped monomers comprise one or more        of the group consisting of        1,3,4,6-tetrakis(methoxymethyl)glycoluril,        N,N,N′,N′,N″,N″-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine,        tetra(methoxymethyl) urea and di(methoxymethyl) urea. In another        variation, an aprotic NOSDS is chosen such as but not limited to        DMSO that also solubilizes the surface of urea granules allowing        the crosslinking action to include the surface of urea allowing        the coating to be chemical bonded to the surface of the urea        granule. In a variation, a protic NOSDS can be added to improve        the coating properties such as but not limited to viscosity and        hydrophobicity.

Additionally, the delivery formulations of the present invention maycontain one or more of the following:

-   -   a food coloring or dye that may be used to improve the visual        evidence of complete coverage and serve as a visual marker;    -   scents or masking agents to improve the odor of the        formulations;    -   Nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules; and    -   Buffering agents.    -   Catalyst(s) to improve reaction completion

In an embodiment, an aprotic NOSDS comprising of one or more aproticsolvents from the group consisting of 1) Dimethyl Sulfoxide and/or 2)dialkyl, diaryl, or alkylaryl sulfoxide(s) having the formula:

R₁S(O)_(x)R₂

-   -   wherein R₁ and R₂ are each independently a C₁₋₆ alkylene group,        an aryl group, or C₁₋₃alkylenearyl group or R₁ and R₂ with the        sulfur to which they are attached form a 4 to 8 membered ring        wherein R₁ and R₂ together are a C₁₋₆ alkylene group which        optionally contains one or more atoms selected from the group        consisting of O, S, Se, Te, N, and P in the ring and x is 1 or        2.        3) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate, 4) one or more polyols capped with acetate        or formate wherein the polyol portion selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and glycerin, 5) one or more        alkylene glycol alkyl ethers acetates selected from the group        consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and/or tripropylene        glycol butyl ether acetate and, 6) isophorone, 7) one or more        diesters consisting of dimethylsuccinate, dimethyl adipate,        diethyl glutarate, and dimethyl glutarate, 8)        dimethylacetamide, 9) dimethylformamide, 10)        dimethyl-2-imidazolidinone, 11) 1-Methyl-2-pyrrolidone, 12)        hexamethylphosphoramide, 13) 1,2-dimethyloxyethane, 14)        2-methoxyethyl ether, 15)cyclohexylpyrrolidone and 16) limonene        can serve as the reaction medium for the formation of        biodegradable, hydrophobic polymers that are the reaction        product of aldehyde(s) and nitrogen containing compounds In an        embodiment the aldehyde(s) comprise one or more of the group        consisting of:

-   -   Q is: O, S    -   Where R¹¹ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —CH═CH₂,        —C₄H₃O, —C₇H₇, —C₆H₅, —C₆H₁₁, CHO, C₂H₃O, C₃H₅O, C₄H₇O, C₇H₅O or        —R¹²O₂R¹³,    -   Where R¹² is: —C, —C₂H₂, —C₃H₄, —C₄H₆, —C₅H₈, —C₆H₁₀    -   Where R¹³ is: —H, CH₃, C₂H₃, C₃H₇, C₄H₉        and nitrogen containing compounds comprising one or more of the        group consisting of

-   -   A is: O, S    -   where R¹⁴ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(a)NH₂        -   Where a is an integer: 1-10    -   where R¹⁵ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(b)NH₂        -   Where b is an integer: 1-10    -   where R¹⁶ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(c)NH₂        -   Where c is an integer: 1-10    -   where R¹⁷ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(d)NH₂        -   Where d is an integer: 1-10            and

and their tautomeric forms and

-   where X₁ is: —NHR¹⁸, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   Where R¹⁸ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂,    -   C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅-   where X₂ is: —NHR¹⁹, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   Where R¹⁹ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂,    -   —C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅-   where X₃ is: —NHR²⁰, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   Where R²⁰ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂,    -   —C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅-   and-   NH₂CO—R²¹-   Where R²¹ is an alkyl radical CH3 to —C17H35    -   In a variation, those skilled in the art can add a catalyst such        as; methane sulfonic acid, sulfuric acid, para-toluene sulfonic        acid. phosphoric acid and methane phosphonic acid to the coating        formulation to improve reactivity and conversion. In a variation        an aldehyde can be reacted with a nitrogen containing compound        within an aprotic NOSDS to form a new monomer. A non-limiting        example would be the chemical        Tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione from the        reaction of 2 moles of urea and one mole of ethandialal and        represented by the structure:

In another variation, the monomeric reaction product of an aldehyde anda nitrogen containing compound can be capped with an C₁-C₄ alkanol grouputilizing an aprotic NOSDS as a reaction medium creating a lowtemperature crosslinking product.

Non-limiting examples would be 1,3,4,6-Tetrakis(methoxymethyl)glycolurilfrom the reaction of one mole ofTetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione with four moles ofmethanal and then capping with four moles of methanol.

N,N,N′,N′,N″,N″-Hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triaminefrom the reaction of one mole of 1,3,5-triazine-2,4,6-triamine with 6moles of methanal and then capping with six moles of methanol.

Tetra(methoxymethyl) urea from the reaction of 1 mole of urea with fourmole of methanal and then capped with four moles of methanol.

In one embodiment, the biodegradable, hydrophobic polymers that are thereaction product of aldehyde(s) and nitrogen containing compounds formedwithin an aprotic NOSDS that serves as the reaction medium containspolyamines compounds such as but not limited to ethylenediamine,diethylenetriamine, triethylenetetramine tetraethylenepentamine andaminoethylethanolamine and/or polyol compounds such as but not limitedto one or more polyols from the group consisting of trimethylol propane,trimethylol ethane, pentaerythritol, sorbitol and sorbitan, glucose,fructose, galactose, and glycerin, 3) poly(C₁₋₁₀ alkylene) glycols, 4)one or more alkylene glycols from the group consisting of ethylene, 1,3propylene glycol, 1,2 propylene glycol, and butylene glycol, 5)isopropylidene glycerol 6) one or more alkylene glycol alkyl ethers fromthe group consisting of tripropylene glycol methyl ether, tripropyleneglycol butyl ether, dipropylene glycol butyl ether and tripropyleneglycol butyl ether constituting 0.1-5% of its polymer weight in order tomodify the coatings' properties such as hydrophobicity, coverage,flexibility of the formed film.

In one embodiment, the biodegradable, hydrophobic polymers that are thereaction product of aldehyde(s) and nitrogen containing compounds formedwithin an aprotic NOSDS that serves as the reaction medium containssecondary amines such as diethylamine, diethanolamine,methylethanolamine, diisopropanolamine, Methylispropylamine andcyclohexylamine and small molecular weight alcohols such as but notlimited to methanol, ethanol, butanol hexanol to assist in controllingthe molecular weight build of the biodegradable, hydrophobic polymerthrough chain termination.

In a variation, a protic NOSDS can be added to improve the coatingproperties such as but not limited to viscosity and hydrophobicity.

Additionally, the delivery formulations of the present invention maycontain one or more of the following:

-   -   a food coloring or dye that may be used to improve the visual        evidence of complete coverage and serve as a visual marker;    -   scents or masking agents to improve the odor of the        formulations;    -   Nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules; and    -   Buffering agents.    -   Catalyst(s) to improve reaction completion.

In an embodiment, an aprotic NOSDS comprising of one or more aproticsolvents from the group consisting of 1) Dimethyl Sulfoxide and/or 2)dialkyl, diaryl, or alkylaryl sulfoxide(s) having the formula:

R₁S(O)_(x)R₂

-   -   wherein R₁ and R₂ are each independently a C₁₋₆ alkylene group,        an aryl group, or C₁₋₃alkylenearyl group or R₁ and R₂ with the        sulfur to which they are attached form a 4 to 8 membered ring        wherein R₁ and R₂ together are a C₁₋₆ alkylene group which        optionally contains one or more atoms selected from the group        consisting of O, S, Se, Te, N, and P in the ring and x is 1 or        2,        3) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate, 4) one or more polyols capped with acetate        or formate wherein the polyol portion selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and glycerin, 5) one or more        alkylene glycol alkyl ethers acetates selected from the group        consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and/or tripropylene        glycol butyl ether acetate and, 6) isophorone, 7) one or more        diesters consisting of dimethylsuccinate, dimethyl adipate,        diethyl glutarate, and dimethyl glutarate, 8)        dimethylacetamide, 9) dimethylformamide, 10)        dimethyl-2-imidazolidinone, 11) 1-Methyl-2-pyrrolidone, 12)        hexamethylphosphoramide, 13) 1,2-dimethyloxyethane, 14)        2-methoxyethyl ether, 15)cyclohexylpyrrolidone and 16) limonene.

These can serve as the reaction medium for the formation ofbiodegradable, hydrophobic polymers that are the reaction product ofaldehyde(s) and nitrogen containing compounds with a molecular weightrange of 1000-200,000 daltons in a molar ratio of aldehyde groups toaldehyde reactive nitrogens on the nitrogen containing compound of(0.10-0.90)/1.0. The process to make said biodegradable, hydrophobicpolymer involves (1) dissolving the nitrogen containing compound into anaprotic NOSDS at temperatures of 10-140° C. wherein the composition iscooled to 30-60° C. 2) the aldehydes are charged at a rate that controlsthe exotherm with 5-20° C. of the reaction temperature that is 30-90° C.in a molar ratio of aldehyde to aldehyde reactive sites on the nitrogencontaining compound of (0.10-0.90)/1.0.3) The reaction is held at 30-70°C. and at a pH of 7.5-10.0 for 5 to 12 hours until the free formaldehydeis 40,000 to 5,000 ppm's. 4) The reaction is heated to 70-100° C., thepH is adjusted to 4.0-8.0 and held until free formaldehyde is <700 ppm,wherein the composition is cooled to less than 40 C and packaged.

In an embodiment the aldehyde(s) comprise one or more of the groupconsisting of

-   -   methanal, ethanal, propanal, butanal, pentanal, hexanal,        methylethanal, methylpropanal, methylbutanal,        phenylacetaldehyde, benzaldehyde, 2-propenal, 3-oxopropanoic,        2-methyl-3-oxopropanoic acid, 4-oxobutanoic acid, oxoacetic        acid, 5-oxopentanoic acid, 6-oxohexanoic acid, 2-oxopropanal,        cyclohexanal, furfural,    -   methyl esters of 3-oxopropanoic, 2-methyl-3-oxopropanoic acid,        4-oxobutanoic acid, oxoacetic acid, 5-oxopentanoic acid and        6-oxohexanoic acid,    -   ethandial, 1,3-propanedial, butanedial, pentanedial,        phthalaldehyde and methanethial

In a variation the aldehydes comprise one or more from the groupconsisting of the structure:

-   -   Where Q is: O, S    -   Where R¹¹ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —CH═CH₂,        —C₄H₃O, —C₇H₇, —C₆H₅, —C₆H₁₁, CHO, C₂H₃O, C₃H₅O, C₄H₇O, C₇H₅O or        —R¹²O₂R¹³,    -   Where R¹² is: —C, —C₂H₂, —C₃H₄, —C₄H₆, —C₅H₈, —C₆H₁₀    -   Where R¹³ is: —H, CH₃, C₂H₃, C₃H₇, C₄H₉        and nitrogen containing compounds comprising one or more of the        group consisting of:    -   urea, biuret, polyurea, thiourea, methylurea, dimethylurea,        ethylurea, diethylurea, propylurea, dipropylurea, butylurea,        dibutylurea, phenylurea, diphenyl urea, pentylurea,        dipentylurea, hexyl urea, dihexyl urea, methylthiourea,        dimethylthiourea, ethylthiourea, diethylthiourea,        propylthiourea, diporpylthiourea, butylthiourea,        dibutylthiourea, pentylthiourea, dipentylthiourea,        hexylthiourea, dihexylthiourea, phenylthiourea,        diphenylthiourea, cyanamide, dicyandiamide, tricyantriamide,        melamine, hydroxy oxypentyl melamine, methylaminomelamine,        dimethylaminopropylmelamine, 1,3,5-Triazine-2,4,6 triamine,        2,4-diamino-1,3,5-triazine, 2,4-diol-6-Amino-1,3,5-triazine,        2,4-Diamino-6-hydroxy-1,3,5-triazine,        2-Butylamino-4,6-diamino-1,3,5-triazine,        2,4-Diamino-6-methyl-1,3,5-triazine,        2,4-Diamino-6-dimethylamino-1,3,5-triazine,        2-Amino-1,3,5-triazine, ethanamide, propanamide, butanamide,        pentanamide, hexanamide, heptanamide, octanamide, nonanamide,        decanamide, dodecanamide, tetradecanamide, hexadecanamide, and        octadecanamide

In a variation, the nitrogen containing compounds comprising one or moreof the group consisting of the structures:

-   -   Where A is: O, S    -   Where R¹⁴ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(a)NH₂    -   Where a is an integer: 1-10    -   Where R¹⁵ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(b)NH₂    -   Where b is an integer: 1-10    -   Where R¹⁶ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(c)NH₂    -   Where c is an integer: 1-10    -   Where R¹⁷ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(d)NH₂    -   Where d is an integer: 1-10,

and their tautomeric forms,

-   -   Where X₁ is: —NHR¹⁸, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   Where R¹⁸ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂, C₃H₆—N (CH₃)₂, C₂H₄OH, —C₆H₅    -   Where X₂ is: —NHR¹⁹, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   Where R¹⁹ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂, —C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅    -   Where X₃ is: —NHR²⁰, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   Where R²⁰ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂, —C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅

and d)

-   -   NH₂CO—R²¹    -   Where R²¹ is an alkyl radical CH₃ to —C₁₇H₃₅

In a variation, a protic NOSDS can be added to improve the coatingproperties such as but not limited to viscosity and hydrophobicity.

Additionally, the delivery formulations of the present invention maycontain one or more of the following:

-   -   a food coloring or dye that may be used to improve the visual        evidence of complete coverage and serve as a visual marker;    -   scents or masking agents to improve the odor of the        formulations;    -   Nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules; and    -   Buffering agents.    -   Catalyst(s) to improve reaction completion.

In one embodiment, hydrophobic, biodegradable polymers powders are addedto the NOSDS under agitation, In a variation, one can aid in thedissolution of the polymer into the NOSDS by using temperatures of15-140° C.

In another variation one can add a small amount of a surfactant toimprove wetting and dispersion of the polymer into the NOSDS. In anothervariation one can use high shear devices such but not limited to acowles dissolver, rotor/stator high shear units or a homogenizer toimprove the polymer dispersion into NOSDS as well as its physicalproperties such as viscosity. In another variation one can use anycombination of such methods.

In one embodiment one can add a hydrophobic, biodegradable polymer thatis dispersed in a liquid into a NOSDS. In a variation if the liquidsystem does not meet the criteria of NOSDS, it can be displaced with asuitable NOSDS through differential boiling points by temperature and/orreduced pressure.

In one embodiment one skilled in the art can produce a hydrophobic,biodegradable polymer within an aprotic NOSDS. In a variation, theresulting product can be further diluted with a protic NOSDS. In anothervariation, the resulting product can be further diluted with an aproticNOSDS. In another variation, the resulting product can be furtherdiluted with a protic and an aprotic NOSDS

In an embodiment the NOSDS not only provide the solvating property forthe hydrophobic, biodegradable polymer but is also the delivery systemfor the hydrophobic, biodegradable polymers to the surface of fertilizergranules.

In one embodiment, the liquid formulation containing biodegradable,hydrophobic polymers that are the reaction product of aldehyde(s) andnitrogen containing compounds and NOSDS is used to coat a dry granularfertilizer, which is then applied to cropland and turf. The hydrophobiccoating makes the fertilizer more effective in providing nutrients forplant growth over an extended period of time. In a variation, flowmodifiers such as but not limited to silicas, powdered lime or apowdered micronutrient salt can be added to the coated fertilizer toimprove granules' flow properties.

In one embodiment, coated granular fertilizer products containingadditional plant nutrients can be prepared from granular fertilizer, asource or sources of the additional nutrients in powdered form describedbelow. Granular fertilizer can be mixed to distribute the liquid mixtureover the granular fertilizer surface using any commonly used equipmentto co-mingle a liquid with a granular solid. After distribution ofmixture over the granular surface, the additional nutrients in powderedform can be added to the dampened mixture and the resulting combinedingredients can be further mixed to distribute the powdered materials.In an alternate embodiment, the powdered materials may be first mixedwith the granular urea and then the solution can be sprayed onto atumbling bed of the dry ingredients to agglomerate the dry materials.This latter method may be particularly suited to continuous processing.In an embodiment, the formulations use combinations of polar aproticsolvents (sulfoxides, sulfones, dialkyl carbonates) with protic solvents(glycols, triols, and alkanolamines) to produce formulations havingacceptable viscosity levels, hydrophobicity and be relatively non-toxic.

In one embodiment, formulations are used to fluidize the biodegradable,hydrophobic polymers that are the reaction product of aldehyde(s) andnitrogen containing compounds and coat the fertilizer granules with awater-resistance layer, which can impede to dissolution of the watersoluble components of fertilizer and slow down the leaching of nutrientsinto soil.

In one embodiment, biodegradable, hydrophobic polymers that are thereaction product of aldehyde(s) and nitrogen containing compounds willdegrade in the soil and the degradation product becomes a source ofnitrogen fertilizer over time.

The mixing of the materials may be accomplished in a simple mixing tankmixing materials prior to use, using a metering system to injectmaterials simultaneously, or mixing via a spray injection system.

The mixture can be mixed in any common mixing tank, blenders andtumblers or on a conveyer belt. Although the metering of all ingredientscan be based on a weight, it may also be based on a volumetric basis.

A dye or colorant can be added to the mixture to aid in visualassessment of uniform coating during the coating of granular urea.Alternatively, a dye or colorant can be added to the mixture to aid invisual assessment of uniform coating during the coating of urea inaqueous mixtures just prior to application. In one embodiment, thecolorant can include any nontoxic common food dye.

EXAMPLES Example 1

157.43 grams of dicyandiamide is added to 299.4 grams of dimethylsulfoxide, heated under agitation to 60° C. and held at 60° C. untilmixture is clear. The mixture is cooled to 40-45° C. and then 42.17grams of paraformaldehyde is slowly charged. The batch is held at 45-55°C. for 1.5 hours. The batch is then heated to 60° C. over a one hourperiod. After 1 hour, 1.0 grams of methane sulfonic acid/70% is chargedand batch is slowly heated to 100° C. over a 3 hour period. A vacuum of40 mm is applied for 30 minutes until distillation ceased, then batch iscooled to <60° C. and off-loaded. Product is clear and viscous.

Example 2

274.12 grams of dicyandiamide is added to 403.03 grams of dimethylsulfoxide, heated under agitation to 60° C. and held at 60° C. untilmixture is clear. 97.91 grams of paraformaldehyde is slowly charged. Thebatch is held at 60° C. for 9 hours until batch is somewhat clear. Thebatch is then heated to 80° C. over a one hour period. After 1 hour,3.72 grams of methane sulfonic acid/70% is charged and batch is slowlyheated to 100° C. over a 1.5 hour period. The batch is heated to 110° C.and a vacuum of 135-140 mm is pulled for a 15 minute period. The batchis then heated to 120° C., a vacuum of 135-140 mm is applied for 35minutes until distillation ceased, then batch is cooled to <60° C. andoff-loaded. Product is clear and viscous.

Example 3

117.6 grams of dicyandiamide is added to 99.4 grams of dimethylsulfoxide and heated under agitation to 85° C. over a 45 minute period.31.5 grams of paraformaldehyde is charged and then 1.49 grams of methanesulfonic acid/70% is charged. The batch is slowly heated to 150° C. overa 3.5 hour period. The batch is heated to 110° C. and a vacuum of135-140 mm is pulled for a 15 minute period. The batch is cooled to <60°C. and off-loaded. Product is clear and viscous.

Example 4

111.8 grams of cicyandiamide is added to 98.49 grams of dimethylsulfoxide, heated under agitation to 80° C., held at 80C for 1 hr, thenheated to 90° C. and held for 30 minutes. 1.24 grams of KOH (flake) ischarged, then 35.94 grams of paraformaldehyde is slowly charged, thenbatch is cooled to 60-70° C. and held for 17 hours. The batch is thenheated to 100° C. over a 2 hour period. 10.08 grams of methane sulfonicacid/70% is charged and batch is slowly heated to 100° C. over a 1.5hour. The batch is heated to 150° C. over a 3 hour period. The batch isthen cooled to <60° C. and off-loaded. Product is clear and viscous.

Example 5

42.48 grams of dicyandiamide is added to 54.26 grams of dimethylsulfoxide and heated under agitation to 80° C. min a 1.5 hour period.The batch is cooled to 40° C., 2.0 grams of paraformaldehyde is charged,the batch is slowly heated to 80° C. over a 1 hour period and then 0.6gram of methane sulfonic acid/70% is charged. The batch is heated to 90°C. over a 2.25 hour period and 48.8 grams ethylene glycol is added. Thebatch is cooled to <60° C. and off-loaded. Product is turbid withparticles and viscous.

Example 6

47.05 grams of dicyandiamide is added to 50.13 grams of dimethylsulfoxide and heated under agitation to 80° C. min a 1.25 hour period.The batch is cooled to 44° C., 2.22 grams of paraformaldehyde is chargedand the batch is slowly heated to 70° C. over a 1 hour period. The batchis heated to 140° C. over a 2.5 hour period. The batch is cooled to <60°C. and off-loaded. Product is turbid with particles and viscous.

Example 7

31.63 grams of dicyandiamide is added to 33.7 grams of dimethylsulfoxide and heated under agitation to 80° C. min a 0.5 hour period.The batch is cooled to 45° C., 2.0 grams of paraformaldehyde is chargedand the batch is slowly heated to 70° C. over a 1 hour period. The batchis held at 70° C. for 1 hour, then 0.4 grams methane sulfonic acid/70%is charged, mixed at 70° C. for one hour and then the batch is heated to90° C. over a 2 hour period. A vacuum of 29 mm is pulled on the reactorfor 20 minutes, the vacuum is broken, 59.48 grams of ethylene glycol arecharged and mixed for 1 hour. The batch is cooled to <60° C. andoff-loaded. Product is turbid with particles and viscous.

Example 8

67.0 grams of dicyandiamide is added to 67.4 grams of dimethyl sulfoxideand heated under agitation to a minimum of 90° C. for a 1.0 hour period.The batch is cooled to 45° C., 5.32 grams of paraformaldehyde is chargedand the batch is slowly heated to 70° C. over a 7.5 hour period. 0.8grams methane sulfonic acid/70% is charged and mixed at 70° C. for onehour and then the batch is heated to 90° C. over a 1 hour period. 32.27grams of ethylene glycol are charged and mixed for 1 hour. The batch iscooled to <60° C. and off-loaded. Product is turbid with particles andviscous.

Example 9

83.64 grams of dicyandiamide is added to 108.73 grams of dimethylsulfoxide and heated under agitation to 90° C. over a 1.0 hour period.The batch is cooled to 45° C., 6.64 grams of paraformaldehyde is chargedand the batch is slowly heated to 75° C. over a 3.0 hour period. 1.0gram methane sulfonic acid/70% is charged and mixed at 75° C. for 1.5hours and then the batch is heated to 95° C. over a 2 hour period. Avacuum of 20 mm is pulled for 40 minutes, the vacuum is broken and thebatch is cooled to <60° C. and off-loaded. Product is clear and viscous.

Example 10

96.8 grams of dicyandiamide is added to 80 grams of dimethyl sulfoxideand heated under agitation to 90° C. over a 0.75 hour period. The batchis cooled to 45° C., 23.05 grams of paraformaldehyde is charged and thebatch is slowly heated to 70° C. over a 4.5 hour period. The batch isheld at 70° C. for a period of 10 hours. 1.0 gram methane sulfonicacid/70% is charged and mixed at 70° C. for 0.5 hours and then the batchis heated to 95° C. over a 2.25 hour period. A vacuum of 20 mm is pulledfor 40 minutes, the vacuum is broken and the batch is cooled to <60° C.and off-loaded. Product is clear and viscous.

Example 11

82.51 grams of dicyandiamide is added to 107.14 grams of dimethylsulfoxide, heated under agitation to 85° C. and held at 85° C. for 1.25hour period. The batch is cooled to 45° C., 7.39 grams ofparaformaldehyde is charged and the batch is mixed over a 3.5 hourperiod. The batch is heated to 75° C. over a period of 2.5 hours. 1.0gram methane sulfonic acid/70% is charged and mixed at 75° C. for 1.5hours and then the batch is heated to 100° C. over a 2.25 hour period. Avacuum of 50-55 mm is pulled for 30 minutes, the vacuum is broken, 1.97grams of triethanolamine is charged and the batch is cooled to <60° C.and off-loaded. Product is clear and fluid.

Example 12

106.63 grams of dicyandiamide is added to 106.32 grams of dimethylsulfoxide, heated under agitation to 85° C. and held at 85° C. for 1.0hour period. The batch is cooled to 50.8° C., 11.25 grams ofparaformaldehyde is charged, and the batch is mixed over a 1.25 hourperiod. The batch is heated to 85° C. over a period of 5.75 hours. Thebatch is held at 85° C. for a period of 15 hours. Batch was cooled to75° C., 1.27 gram methane sulfonic acid/70% is charged, mixed at 75° C.for 1.5 hours and then the batch is heated to 100° C. over a 2.0 hourperiod. A vacuum of 50-55 mm is pulled for 30 minutes, the vacuum isbroken, 2.55 grams of triethanolamine is charged, and the batch iscooled to <60° C. and off-loaded. Product is hazy and viscous.

Example 13

102.44 grams of dicyandiamide is added to 80 grams of dimethylsulfoxide, heated under agitation to 80° C. and held at temperature fora 1.0 hour period. The batch is cooled to 44.0° C., 14.64 grams ofparaformaldehyde is charged and the batch is mixed over a 0.75 hourperiod. The batch is heated to 85° C. over a period of 2 hours. Thebatch is held at 80° C. for a period of 1 hour. Batch is cooled to 61°C., 0.88 grams methane sulfonic acid/70% is charged, mixed 1 hour andallowed to exotherm to 70° C. The batch is then heated to 100° C. over a3.75 hour period. A vacuum of 45-55 mm is pulled for 30 minutes, thevacuum is broken, 2.04 grams of triethanolamine is charged and the batchis cooled to <60° C. and off-loaded. Product is clear and viscous.

Example 14

138.47 grams of dicyandiamide is added to 120 grams of dimethylsulfoxide, heated under agitation to 80° C., and held at temperature fora 1.0 hour period. The batch is cooled to 60° C., 32.97 grams ofparaformaldehyde is charged, and the batch is mixed over a 1.15 hourperiod. The batch is heated to 80° C. over a period of 2 hours. Thebatch is cooled to 61° C., 2.57 grams methane sulfonic acid/70% ischarged, mixed 1 hour and allowed to exotherm to 70° C. The batch isthen heated to 100° C. over a 2 hour period. A vacuum of 45-55 mm ispulled for 30 minutes, the vacuum is broken, 5.99 grams oftriethanolamine is charged, and the batch is cooled to <60° C. andoff-loaded. Product is clear and viscous.

Example 15

180.18 grams of dicyandiamide is added to 140 grams of dimethylsulfoxide, heated under agitation to 80° C. and held at temperature fora 1.0 hour period. The batch is cooled to 56° C., 19.01 grams ofparaformaldehyde is charged, and the batch is mixed over a 1 hourperiod. The batch is heated 80° C. over a period of 2 hours. The batchis cooled to 60.3° C., 3.25 grams methane sulfonic acid/70% is charged,mixed 1 hour and allowed to exotherm to 70° C. The batch is then heatedto 115° C. over a 6 hour period. A vacuum of 45-55 mm is pulled for 30minutes, the vacuum is broken, 7.56 grams of triethanolamine and 17.6grams of tripropylene glycol monomethyl ether are charged and the batchis cooled to <60° C. and off-loaded. Product is clear and viscous.

Example 16

174.57 grams of dicyandiamide is added to 140 grams of dimethylsulfoxide, heated under agitation to 80° C. and held at temperature fora 1.0 hour period. The batch is cooled to 55° C., 24.94 grams ofparaformaldehyde is charged, and the batch is mixed over a 1.15 hourperiod. The batch is heated 80° C. over a period of 2 hours. The batchis cooled to 60° C., 3.99 grams methane sulfonic acid/70% is charged,mixed 1 hour and allowed to exotherm to 70° C. The batch is then heatedto 115° C. over a 4 hour period. A vacuum of 45-55 mm is pulled for 30minutes, the vacuum is broken, 6.50 grams of triethanolamine is chargedand the batch is cooled to <60° C. and off-loaded. Product is clear andviscous.

Example 17

100.45 grams of urea is added to 80 grams of dimethyl sulfoxide, heatedunder agitation to 80° C. and held at temperature for 1.0 hour period.The batch is cooled to 53.6° C., 2 drops of 45% KOH and 16.74 grams ofparaformaldehyde are charged and the batch is mixed over a 1.15 hourperiod. The batch is heated 75° C. over a period of 2 hours. The batchis held at 75° C. for an additional period of 1 hour. The batch iscooled to 44.7° C., 3.99 grams methane sulfonic acid/70% is charged,mixed 1 hour and allowed to exotherm to 60.7° C. The batch is thenheated to 90° C. over a 2 hour period. A vacuum of 45-55 mm is pulledfor 30 minutes, the vacuum is broken, 1.88 grams of triethanolamine ischarged, and the batch is cooled to <60° C. and off-loaded. Product isopaque and very viscous.

Example 18

142.12 grams of urea is added to 99.58 grams of dimethyl sulfoxide,heated under agitation to 80° C. min and held at temperature for a 1.0hour period. The batch is cooled to 45° C., 2 drops of 45% KOH and 60.06grams of paraformaldehyde are charged and the batch is mixed over a 1.15hour period. The batch is heated 70° C. over a period of 2 hours. Thebatch is held at 70° C. for an additional period of 1 hour. 128 grams ofmethanol is charged to the batch. The batch is then heated to reflux forone hour and then cooled to 44.7° C. The pH is adjusted to 5.5-6.5 withnitric acid/20% and the batch is allowed to exotherm to reflux. After 45minutes, heat is returned to the reactor for 1 hour to maintain reflux.The pH is adjusted to 8.8-9.5 with 45% KOH and methanol/water isremoved. When distillation ceases the batch is placed under vacuum of<40 mm until distillation ceases. The batch is cooled to 45° C. The pHis adjusted to 5.5-6.5 with nitric acid/20% and the batch is allowed toexotherm to reflux. After 10 minutes, heat is returned to the reactorfor 1 hour to maintain reflux. The pH is adjusted to 8.8-9.5 with 45%KOH and methanol/water is removed. When distillation ceases the batch isplaced under vacuum of <40 mm until distillation ceases. The batch iscooled to 45° C. The pH is adjusted to 5.5-6.5 with nitric acid/20% andthe batch is allowed to exotherm to reflux. After 10 minutes, heat isreturned to the reactor for 1 hour to maintain reflux. The pH isadjusted to 8.8-9.5 with 45% KOH and methanol/water is removed. Whendistillation ceases, the batch is placed under vacuum of <40 mm untildistillation ceases. The batch is cooled to <60° C. and off-loaded.Product is opaque and very viscous. Clear at 70-90° C.

Many of these hydrophobic, biodegradable polymers that have beenproduced within the NOSDS, dimethyl sulfoxide are high viscosity and afew demonstrate poor shelf stability. Formulations have been preparedutilizing other NOSDSs to impart improvements in these properties. Thefollowing table illustrates samples that were formulated using standardoverhead mixing and temperatures of 40-120° C.

Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ingredients19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 Example 2 62.2 62.6 62.662.6 62.6 62.6 62.6 62.6 62.6 Example 6 62.1 62.1 62.1 Example 11 85.075.0 Example 17 50.0 TPM 15.0 25.0 DPG 37.9 DMSO 37.8 50.0 DPMAc DimGlut37.8 Ethyl 37.4 Lactate IPDG 37.4 DBE-3 37.4 PropCarb 37.4 37.9 HexGly37.4 PG 37.4 EG 37.4 ButCarb 37.9 Appearance Clr Clr P Clr Clr Clr ClrClr P Clr Clr Clr P Clr Clr Freeze/thaw G G DNR G G G G G DNR G G G DNRG G Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ingredients34 35 36 37 38 39 40 41 42 43 44 45 46 47 Example 11 85.0 75.0 Example12 50.0 50.0 50.0 50.0 Example 13 87.0 64.0 95.0 50.0 75.0 Example 1595.0 Example 16 50.0 75.0 TPM 50.0 36.0 5.0 5 DPG 15.0 25.0 50.0 50.0 2550 25 DMSO DPMAc 13.0 L-62 50.0 ButCarb 50.0 Appearance Clr Clr Clr ClrClr Clr Clr Clr Clr Clr Clr Clr Clr Clr Freeze/thaw G G G G G G G G G GG G G G Clr = Clear P = Poor G = Good DNR = Did not Run TPM:Tripropyleneglycol methyl ether DPG: Dirpopylene Glycol DMSO: DimethylSulfoxide DPMAc: dipropyleneglycol methyl ether acetate DimGlut:Dimethyl Glutarate IPDG: Isopropylideneglycerol DBE-3: dimethyl adipate,glutarate and succinate PropCarb: propylene Carbonate HexGly: HexyleneGlycol PG: propylene glycol EG: ethylene glycol L-62: EO/PO blockedcopolymer ButCarb: Butylene Carbonate

The following examples are formulations of the hydrophobic,biodegradable polymers that have been produced within the dimethylsulfoxide and formulated with other aprotic and protic solvents andbiologically active agents such as urease and nitrification inhibitors.

Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex Ingredients 48 49 50 51 52 53 5455 56 57 Example 32 95.0 Example 33 93.0 Example 34 93.0 Example 35 93.0Example 36 93.0 Example 37 93 Example 11 85 Example 44 90.9 95 95N-(n-butyl) 5.0 7.0 7.0 7.0 7.0 7.0 15 thiophosphoric triamide2-Chloro-6- 9.1 (trichloromethyl)pyridine aminomethyl(N-n 5butylaminomethyl) phosphinic acid aminomethyl(N-n 5 hexylaminomethyl)phosphinic acid Appearance Clr Clr Clr Clr Clr Clr Clr Clr Clr ClrFreeze/thaw G G G G G G G G G G Clr = Clear P = Poor G = Good DNR = Didnot Run Note: dicyandiamide was not included in these experiments sincemany of the samples already possessed free dicyandiamide such as example11 and example 12.

As shown by the above examples, biologically active agents can be addedto the hydrophobic, biodegradable polymers that have been producedwithin the NOSDS, dimethyl sulfoxide and further can be added to thehydrophobic, biodegradable polymers that have been produced within theNOSDS, dimethyl sulfoxide and further formulated with protic and aproticsolvents to produce stable products.

A number of the examples were tested for improving urea's resistance todissolution. The experimental samples were applied to urea usingstandard overhead mixer with an anchor agitator. The amount of thesample to charge was determined by the specific gravity of the sampletimes the volumetric treatment level. For example: Determining theamount of Example 32 to be charged at a rate of 3 quarts/ton of urea:

-   -   Specific gravity=1.163 gm/ml=9.68 lb/gal    -   At an application level of 3 quart/ton of urea=7.26 lbs of        Example 32/2000 lbs of urea    -   The application level would be 0.363% of Example 32

The 200 grams of urea was placed in a vessel, agitation was set so notto sling the urea out of the vessel and the calculated amount of theexperimental sample was dripped onto the agitating urea. Aftercompleting the sample addition, the urea was agitated for an additionalminute to insure uniform coverage. Some samples required approximately1-2% of hydrophobic silica as a flow aide to improve the flow propertiesof the treated urea. The treated urea was set aside for 24 hours ineither at room temperature or at 50° C. The dissolution test method wasperformed in 100 mls of distilled water in a 150 ml beaker by droppingone granule of either treated or untreated urea into the water. Time wasmeasured from when the urea entered the water until it had dissolved.

Example 58

Treatment level 4 quarts/ton Experimental % improvement over Sample #urea dissolution Ex 19 13% Ex 24 17% Ex 25 33% Ex 22 42%

Example 59

Treatment level 3 quarts/ton 50 C. for 3 days Experimental % improvementover Sample # urea dissolution Ex 31 + silica 77% Ex 31 51% Ex 36 39% Ex38 + silica 82% Ex 38 + silica 72% Ex 39 46%

Example 60

Treatment level 3 quarts/ton 50 C. for 3 days Experimental % improvementover Sample # urea dissolution Ex 32 41% Ex 33 33% Ex 34 34% Ex 35 77%

A couple of experimental samples containing biological active agentswere tested for improving urea's resistance to dissolution utilizing theprevious testing procedure.

Treatment level 3 quarts/ton 50 C. for 3 days Experimental % improvementover Sample # urea Ex 49 48% Ex 50 22% Ex 57 25%

Example 61

grams of DMSO and 82.26 grams of DCD were charged to a reaction flask,heated to 86.4° C., held until contents were clear and then cooled to50° C. 7.37 grams of paraformaldehyde were charged and then mixed for 30minutes. The contents were then heated to 86.2° C. over a 3 hour periodand held until the solution became clear. The contents were cooled to59.9° C. and then 1.19 grams of methane sulfonic acid/70% were added.The contents were mixed for 5 minutes and then the contents were slowlyheated to 110° C. over a 2.5 hr period of time. At 110° C., a vacuum of45-65 mm Hg was applied to the reaction flask for 0.5 hrs, the vacuumwas broken with nitrogen and then the contents were cooled to <45° C.and packaged. The amount of distillate collected was 11.26 grams, theyield 178.82 grams and the calculated amount of DCD was 46.21%.

Example 62

106.82 grams of DMSO and 82.26 grams of DCD were charged to a reactionflask, heated to 95° C., held until contents were clear and then cooledto 65° C. 7.37 grams of paraformaldehyde were charged and the contentswere then heated to 81° C. over a 0.75 hour period and held 1.3 hrsuntil the solution became clear. The contents were cooled to 41.7° C.and then 1.19 grams of methane sulfonic acid/70% were added. Thecontents were mixed for 5 minutes and then the contents were slowlyheated to 110° C. over a 2.1 hr period of time. At 110° C., a vacuum of54-65 mm Hg was applied to the reaction flask for 0.8 hr, the vacuum wasbroken by nitrogen, 2.37 grams of triethanolamine/99% were charged andthen the contents were cooled to <45° C. and packaged. The yield 189.08grams and the calculated amount of DCD was 43.5%.

Example 63

101.6 grams of DMSO and 87.05 grams of DCD were charged to a reactionflask, heated to 110° C., held until contents were clear and then cooledto 60° C. 7.80 grams of paraformaldehyde were charged and then thecontents were heated to 85° C. over a 8.5 hour period. 1.19 grams ofmethane sulfonic acid/70% were added. The contents were mixed for 5minutes and then the contents were slowly heated to 95° C. over a 2 hrperiod of time. At 95° C., a vacuum of 35-50 mm Hg was applied to thereaction flask for 0.5 hr, the vacuum was broken by nitrogen and thenthe contents were cooled to <45° C. and packaged. The yield 189.4 gramsand the calculated amount of DCD was 45.96%.

Example 64

140 grams of DMSO and 174.57 grams of DCD were charged to a reactionflask, heated to 82° C., held for 1 hr and then cooled to 65° C. 24.94grams of paraformaldehyde were charged, the contents were then heated to75° C. and held at temperature for 3.5 hrs. 3.99 grams of methanesulfonic acid/70% were added over a 0.75 hr period, the contents weremixed for 5 minutes and then the contents were slowly heated to 110° C.over a 2.1 hr period of time. At 110° C., a vacuum was applied to thereaction flask for 0.8 hr, the vacuum was broken by nitrogen and thenthe contents were cooled to <45° C. and packaged. The yield 309.5 gramsand the calculated amount of DCD was 57.24%.

Example 65

140 grams of DMSO and 162.12 grams of DCD were charged to a reactionflask, heated to 82° C. and held for 1 hr and then cooled to 65° C.38.60 grams of paraformaldehyde were charged, mixed for 0.5 hr and thecontents were then heated to 85° C. over a 3.75 hr period and held attemperature for 0.75 hrs. 3.53 grams of methane sulfonic acid/70% wereadded over a 0.3 hr period, the contents were mixed for 5 minutes andthen the contents were slowly heated to 110° C. over a 3.8 hr period oftime. At 110° C., a vacuum of 27-31 mm Hg was applied to the reactionflask for 0.7 hr, the vacuum was broken by nitrogen and then thecontents were cooled to <45° C. and packaged. The amount of distillatecollected was 33.15 grams, the yield 299.03 grams and the calculatedamount of DCD was 53.33%.

Example 66

140 grams of DMSO and 153.37 grams of DCD were charged to a reactionflask, heated to 85° C., held for 1 hr. 45.65 grams of paraformaldehydewere charged, mixed for 0.5 hr and then the contents were then heated to85° C. over a 3.75 hr period and held at temperature for 1.25 hrs. 4.17grams of methane sulfonic acid/70% were added over a 0.25 hr period, thecontents were mixed for 5 minutes and then the contents were slowlyheated to 110° C. over a 4.5 hr period of time. At 110° C., a vacuum of23.6-31 mm Hg was applied to the reaction flask for 0.5 hr, the vacuumwas broken by nitrogen and then the contents were cooled to <45° C. andpackaged. The amount of distillate collected was 46.09 grams, the yield287.27 grams and the calculated amount of DCD was 52.35%.

Example 67

181.18 grams of DMSO and 144.87 grams of DCD were charged to a reactionflask, heated to 85° C., held for 1 hr and then cooled to 65° C. 13.45grams of paraformaldehyde were charged, mixed for 0.5 hr and thecontents were then heated to 110° C. over a 9.5 hr period and held attemperature for 0.5 hrs. No methane sulfonic acid/70% was added. Thecontents were cooled to 90° C. over a 0.5 hr period of time. At 90° C.,a vacuum of 28-31 mm Hg was applied to the reaction flask for 0.5 hr,the vacuum was broken by nitrogen and then the contents were cooled to<45° C. and packaged. The amount of distillate collected was 49.27grams,the yield 329.93 grams and the calculated amount of DCD was 43.91%.

Example 68

181.18 grams of DMSO and 144.87 grams of DCD were charged to a reactionflask, heated to 80° C. and held for 1 hr. At 80° C., 13.45 grams ofparaformaldehyde were charged, mixed for 0.5 hr and the contents werethen heated to 85° C. and held at temperature for 8.5 hrs. No methanesulfonic acid/70% was added. The contents were heated to 90-95° C. andheld at temperature for a 12 hr period of time. At 90° C., a vacuum of22.3-28.0 mm Hg was applied to the reaction flask for 1.0 hr, the vacuumwas broken by nitrogen and then the contents were cooled to <45° C. andpackaged. The amount of distillate collected was 11.36grams, the yield322.35 grams and the calculated amount of DCD was 44.95%.

Example 69

179.47 grams of DMSO and 144.28 grams of DCD were charged to a reactionflask and heated to 45° C. and an inert vessel was achieved by pulling avacuum then breaking with nitrogen and repeating this procedure 2 times.13.74 grams of paraformaldehyde were charged and mixed for 0.5 hr andthe contents were then heated to 90° C. over a 9 hr period. At 90° C.2.04 grams of methane sulfonic acid/70% were added. The contents weremixed for 5 minutes and then the contents were slowly heated to 95° C.and held for a 2 hr period of time. At 95° C., a vacuum of 28 mm Hg wasapplied to the reaction flask for 0.5 hr, the vacuum was broken bynitrogen and then the contents were cooled to <45° C. and packaged. Theamount of distillate collected was 11.55 grams, the yield 322.37 gramsand the calculated amount of DCD was 44.76%.

Example 70

179.47 grams of DMSO and 144.28 grams of DCD were charged to a reactionflask and heated to 40° C., an inert vessel was achieved by pulling avacuum then breaking with nitrogen and repeating this procedure 2 times.13.74 grams of paraformaldehyde were charged and mixed for 0.5 hr andthe contents were then heated to 112.6° C. over a 6.5 hr period. Nomethane sulfonic acid/70% was added. At 110° C., a vacuum of 2 mm Hg wasapplied to the reaction flask for 0.5 hr, the vacuum was broken bynitrogen and then the contents were cooled to <45° C. and packaged. Theamount of distillate collected was 19.17 grams, the yield 314.18 gramsand the calculated amount of DCD was 45.65%.

Example 71

179.47 grams of DMSO, 13.74 grams of paraformaldehyde and 144.28 gramsof DCD were charged to a reaction flask at a temperature of 35° C., aninert vessel was achieved by pulling a vacuum then breaking withnitrogen and repeating this procedure 2 times. mixed for 0.5 hr and thecontents were then heated to 100° C. over a 2 hr period and held at 100°C. for a period of 5 hrs. No methane sulfonic acid/70% was added. At100° C., a vacuum was applied to the reaction flask for 0.7 hr, thevacuum was broken by nitrogen and then the contents were cooled to <45°C. and packaged. The amount of distillate collected was 18.4 grams, theyield 313.8 grams and the calculated amount of DCD was 45.70%.

Example 72

179.47 grams of DMSO, 13.74 grams of paraformaldehyde and 144.28 gramsof DCD were charged to a reaction flask at a temperature of 35° C., aninert vessel was achieved by pulling a vacuum then breaking withnitrogen and repeating this procedure 2 times. mixed for 0.5 hr and thecontents were then heated to 80° C. over a 2 hr period and held at 80°C. for a period of 7 hrs. At 80° C. 2.04 grams of methane sulfonicacid/70% were added. The contents were mixed for 5 minutes and then thecontents were mixed at 80° C. for a 1 hr period of time. The contentswere then heated to 90 C and a vacuum was applied to the reaction flaskfor a period of 2 hr, the vacuum was broken by nitrogen and then thecontents were cooled to <45° C. and packaged. The amount of distillatecollected was 13.47 grams, the yield 320.65 grams and the calculatedamount of DCD was 46.39%.

Example 73

193.68 grams of DMSO and 104.19 grams of DCD were charged to a reactionflask at a temperature of 18° C., an inert vessel was achieved bypulling a vacuum then breaking with nitrogen and repeating thisprocedure 2 times. 16.91 grams of paraformaldehyde charged, mixed for0.25 hr and the contents were then heated to 70° C. over a 0.5 hr periodand held at 70° C. for a period of 13 hrs. No methane sulfonic acid/70%was added. The contents were then heated to 90 C and held for 4 hours.35.22 grams of DCD were charged a vacuum of 15 mm Hg was applied to thereaction flask for a period of 1.5 hr while the temperature was allowedto cooled to 80° C. The vacuum was broken by nitrogen and then thecontents were cooled to <45° C. and packaged. The amount of distillatecollected was 15.86 grams, the yield was 329.73 grams and the calculatedamount of DCD was 42.12%.

Example 74

204.23 grams of DMSO and 120.84 grams of DCD were charged to a reactionflask at a temperature of 18° C., an inert vessel was achieved bypulling a vacuum then breaking with nitrogen and repeating thisprocedure 2 times. 19.62 grams of paraformaldehyde mixed for 0.25 hr andthe contents were then heated to 70° C. over a 0.5 hr period and held at70° C. for a period of 3.5 hrs. At 70° C., 2.08 grams of methanesulfonic acid/70% were added. The contents were mixed for 5 minutes andthen the contents were mixed at 70° C. for a 1 hr period of time. Thecontents were then heated to 80 C and held for 3 hours at temperatureand under a vacuum. The vacuum was broken by nitrogen and then thecontents were cooled to <45° C. and packaged. The amount of distillatecollected was 17.89 grams, the yield was 326.32 grams with a strongsmell of formaldehyde and the calculated amount of DCD was 36.69%.

Example 75

204.23 grams of DMSO and 120.84 grams of DCD were charged to a reactionflask at a temperature of 18° C., an inert vessel was achieved bypulling a vacuum then breaking with nitrogen and repeating thisprocedure 2 times, charged 19.62 grams of paraformaldehyde mixed for0.25 hr and the contents were then heated to 84.3° C. over a 0.5 hrperiod and held at 80° C. for a period of 3.5 hrs. At 80° C., 2.08 gramsof methane sulfonic acid/70% were added and mixed for 1 hr, At 80° C.,the contents were placed under a vacuum of 15-30 mm Hg and held at 80°C. for a period of 1.5 hr. The contents were then heated to 90 C andheld for 3 hours at temperature and under a vacuum. The vacuum wasbroken by nitrogen, 3.23 grams of triethanolamine/99% was charged andthen the contents were cooled to <45° C. and packaged. The amount ofdistillate collected was 28.93 grams, the yield was 315.99 grams and thecalculated amount of DCD was 38.24%.

Example 76

754.11 grams of DMSO and 619.74 grams of DCD were charged to a reactionflask at a temperature of 20° C., an inert vessel was achieved bypulling a vacuum then breaking with nitrogen and repeating thisprocedure 2 times, charged 63.19 grams of paraformaldehyde mixed for0.25 hr and the contents were then heated to 80° C. over a 0.75 hrperiod and held at 80° C. for a period of 6 hrs. At 80° C., 8.67 gramsof methane sulfonic acid/70% were added. The contents were mixed for 5minutes and then the contents were placed under a vacuum of <50 mm Hgfor period of a 1 hr. The contents were then heated to 90-95° C. andheld for 4.5 hours at temperature and under a vacuum. The vacuum wasbroken by nitrogen, a portion was removed for analytical purpose (codedExample 76 base) and then 9.42 grams of triethanolamine/99% and 29.95grams of a polysuccinimide were charged and mixed until homogeneous. Thecontents were cooled to <45° C. and packaged. The data of the example 76base is the amount of distillate collected was 42.09 grams, the yieldwas 1425.28 grams and the calculated amount of DCD was 44.95%.

Example 77

71.01 grams of DMSO and 66.72 grams of 3,5-dimethylpyrazole were chargedto a reaction flask at a temperature of 18° C., an inert vessel wasachieved by pulling a vacuum then breaking with nitrogen and repeatingthis procedure 2 times, charged 10.42 grams of paraformaldehyde mixedfor 0.25 hr and the contents were then heated to 80.0° C. over a 4.0 hrperiod. At 80° C., 0.89 grams of methane sulfonic acid/70% was added andmixed for 1 hr. The contents were then heated to 110 C over a period oftime of 2.5 hrs and held for 0.5 hours at temperature. Contents werecooled to 90° C. and placed under a vacuum of 29 mm Hg for a period oftime of 1.5hrs. The vacuum was broken by nitrogen and then the contentswere cooled to <45° C. and packaged. The amount of distillate collectedwas 9.55 grams and the yield was 135.28 .

Example 78

75.28 grams of DMSO and 61.87 grams of DCD were charged to a reactionflask at a temperature of 20.4° C., an inert vessel was achieved bypulling a vacuum then breaking with nitrogen and repeating thisprocedure 2 times, charged 11.05 grams of paraformaldehyde mixed for0.25 hr and the contents were then heated to 80° C. held at 80° C. overa 3.0 hr period of time. At 80° C., 0.87 grams of methane sulfonicacid/70% was added and mixed for 1 hr. At 80° C., the contents wereplaced under a vacuum of 15-30 mm Hg and the contents were then heatedto 90 C and held for 0.3 hours at temperature and under a vacuum. Thevacuum was broken by nitrogen, and then the contents were cooled to <45°C. and packaged. The amount of distillate collected was 9.45 grams, theyield was 132.71 grams with a slight smell of formaldehyde and thecalculated amount of DCD was 46.62%.

Example 79

70.44 grams of DMSO and 59.88 grams of DCD were charged to a reactionflask at a temperature of 18.6° C., an inert vessel was achieved bypulling a vacuum then breaking with nitrogen and repeating thisprocedure 2 times, charged 17.82 grams of paraformaldehyde mixed for0.25 hr and the contents were then heated to 80° C. held at 80° C. overa 2.0 hr period of time. At 80° C., 0.89 grams of methane sulfonicacid/70% was added and the contents were placed under a vacuum of 16-30mm Hg for a period of 0.5 hrs. The contents were then heated to 90 C andheld for a period of 2 hours at temperature and under a vacuum of 16 mmHg. The vacuum was broken by nitrogen, the vessel was placed undervacuum and then the vacuum was broken by a hard sparge of nitrogen (wasrepeated 3 times) and then the contents were cooled to <45° C. andpackaged. The amount of distillate collected was 12.01 grams, the yieldwas 129.0 grams and the calculated amount of DCD was 46.12%.

Example 80

23.67 grams of sulfolane and 22.24 grams of 3,5-dimethylpyrazole werecharged to a reaction flask at a temperature of 18° C., 10.42 grams ofparaformaldehyde were charged and mixed for 0.25 hr and the contentswere then heated to 80.0° C. over a 2.0 hr period. At 80° C., 0.30 gramsof methane sulfonic acid/70% was added and mixed for 1 hr. The contentswere then heated to 100 C over a period of time of 1 hr and held for 0.5hours at temperature. Contents were placed under a vacuum of 19 mm Hgfor a period of time of 0.5 hrs. The vacuum was broken by nitrogen andthen the contents were cooled to <45° C. and packaged. The amount ofdistillate collected was 0 grams and the yield was 47.7 grams.

Example 81

64.72 grams of DMSO, 55.03 grams of DCD and 12.16 grams of3,5-dimethylpyrazole were charged to a reaction flask at a temperatureof 20.4° C., an inert vessel was achieved by pulling a vacuum thenbreaking with nitrogen and repeating this procedure 2 times, charged19.44 grams of paraformaldehyde, contents were mixed for 0.25 hr and thecontents were then heated to 80° C. held at 80° C. over a 2.0 hr periodof time. Contents were cooled to 60° C. and 0.91 grams of methanesulfonic acid/70% was added, the contents were placed under a vacuum of15 mm Hg and the contents were then heated to 90 C and held for 3 hoursat temperature and under a vacuum. The vacuum was broken by nitrogen,0.99 grams of triethanolamine/99% were charged and then the contentswere cooled to <45° C. and packaged. The amount of distillate collectedwas 13.94 grams, the yield was 126.98 grams and the calculated amount ofDCD was 43.58%.

Example 82

77.74 grams of DMSO and 63.88 grams of DCD were charged to a reactionflask at a temperature of 15.4° C., an inert vessel was achieved bypulling a vacuum then breaking with nitrogen and repeating thisprocedure 2 times, charged 6.51 grams of paraformaldehyde mixed for 0.25hr and the contents were then heated to 80° C. held at 80° C. over a 3.0hr period of time. Contents were cooled 40° C., 0.89 grams of pTSA wasadded and the contents were placed under a vacuum of 29-30 mm Hg. Thecontents were then heated to 90 C and held for a period of 2 hours attemperature and under a vacuum of 21 mm Hg. The vacuum was broken bynitrogen, ½ of the contents were removed and coded Example 82 and thenExample 82 was cooled to <45° C. and packaged. The amount of distillatecollected was 6.48 grams, the yield was 139.48 grams and the calculatedamount of DCD was 45.8%. The remaining content was continued as Example83.

Example 83

The remaining contents of Example 82 in the reaction flask were heatedto 90-95° C. and 10 grams of distilled water were added. The contentswere held at 90-90° C. for a period of 2 hrs and then placed undervacuum until charged water was removed (approx. 11.6 grams of distillaterecovered). The contents were then cooled and packaged.

Example 84

Heat 51.6 grams of DMSO to 60° C. under agitation and then charge 48.4grams of 3,5-dimethylpyrazole (DMP). Mix @ 60° C. until clear. Packagein a seal container and maintain sample @ 50-70° C. for clarity andhomogeneity

Example 85

Aluminum weigh pans were weighed and the weight recorded. Approximately2 grams of sample were weighed into aluminum weigh pan and then placedin an oven @60° C. for 24 hours. After 24 hours, the sample in thealuminum weigh pan was removed from the oven and weighed. The weightswere compared and percentage of non-volatile matter was calculated asshown in Chart 1.

CHART 1 Weight pan Sample after 24 hrs % Example wt initial wtdifference @60° C. remaining *DMSO 2.645 3.674 1.029 2.645   0% Example77 2.644 4.874 2.230 3.251 27.22%  Example 84 2.633 4.836 2.203 2.6420.41% *DMSO was 0% remaining after 12 hrs

The results of the volatility test show that the DMP oligomer fromexample 67 has >50% weight retention versus unreacted DMP from Example84. The >50% is based on the results that show DMSO has completelyvolatilized in 24 hours and the footnote that states this volatilityoccurred after 12 hours.

Example 86

90.9 grams of Example 61 were blended with 9.1 grams of propylene glycolat 30° C. and then packaged. Sample appearance was clear.

Example 87

90.9 grams of Example 61 were blended with 9.1 grams of ethylene glycolat 30° C. and then packaged. Sample appearance was clear.

Example 88

91.4 grams of Example 63 were blended with 8.62 grams of DMSO at 30° C.and then packaged. Sample appearance was clear.

Example 89

91.4 grams of Example 63 were blended at 30° C. with 8.62 grams a 50%ammonium neutralized polyaspartate (polyaspartate polymer weight3000-5000 grams/mole) dispersed in DMSO and then packaged. Sampleappearance was clear.

Example 90

30 grams of Example 64 were blended with 44.45 grams of DMSO, 0.3 gramsof triethanolamine, 25.25 grams of DCD were heated to 80° C. mixed untilclear, cooled to <40 C and then packaged. Sample appearance was clear.

Example 91

30 grams of Example 65 were blended with 43.54 grams of DMSO, 0.3 gramsof triethanolamine, 26.16 grams of DCD were heated to 80° C. mixed untilclear, cooled to <40° C. and then packaged. Sample appearance was clear.

Example 92

78.6 grams of Example 64 were blended with 21.4 grams of DMSO at 30° C.and then packaged. Sample appearance was clear.

Example 93

78.6 grams of Example 64 were blended with 21.4 grams of ethylene glycolat 30° C. and then packaged. Sample appearance was clear.

Example 94

78.6 grams of Example 64 were blended with 21.4 grams of polyethyleneglycol at 30° C. and then packaged. Sample appearance was clear.

Example 95

83 grams of Example 65 were blended with 17 grams of DMSO at 30° C. andthen packaged. Sample appearance was clear.

Example 96

85.13 grams of Example 65 were blended with 14.9 grams of DMSO at 30° C.and then packaged. Sample appearance was clear.

Example 97

97 grams of Example 68 were blended with 2 grams of a polysuccinimide(polymer weight 3000-5000 grams/mole) and 1 gram of a solvent dispersedblue dye at 60° C. and cooled and package. Sample appearance was blueand clear.

Example 98

81.84 grams of Example 73 were blended with 0.66 grams of DMSO, and14.50 grams of DCD were heated to 80° C. mixed until clear, cooled to<40 C and then packaged. Sample appearance was clear.

Example 99

30 grams of Example 73 were blended at 30° C. with 70 grams a 50%ammonium neutralized polyaspartate (polyaspartate polymer weight3000-5000 grams/mole) dispersed in DMSO and then packaged. Sampleappearance was clear.

Example 100

41.72 grams of Example 73 were blended with 25 grams of apolysuccinimide (polymer weight 3000-5000 grams/mole) and 33.29 gramsDMSO at 60° C. and cooled and package. Sample appearance was clear.

Example 101

28.57 grams of tripropylene glycol methyl ether were blended with 0.5grams of triethanolamine and 40.0 grams of Example 73 and then heated to40° C. While mixing, 30.93 grams of N-(-n-butyl) thiophosphoric triamidewere added and mixed until all particles were dissolved. The sample wasclear and packaged.

Example 102

Blends in examples 86-101 were evaluated for sample storage stabilityand are listed in Chart 2:

CHART 2 Freeze Stable @ thaw Stable @ Example 25° C. for 7 stable 50° C.for 3 # days (3 times) days 86 Pass Pass Pass 87 Pass Pass Pass 88 PassPass Pass 89 Pass Pass Pass 90 Pass Pass Pass 91 Pass Pass Pass 92 PassPass Pass 93 Pass Pass Pass 94 Pass Pass Pass 95 Pass Pass Pass 96 PassPass Pass 97 Pass Pass Pass 98 Pass Pass Pass 99 Pass Pass Pass 100 PassPass Pass 101 Pass Pass Pass

Evaluation shows that blended formulations have good storage stability.

Example 103

Some of the samples were analyzed for viscosity, pH, formaldehydecontent and dispersibility in distilled water to yield a borderlinetranslucent dispersion. The results as well as the molar ratio of thereactants are as shown in Chart 3:

CHART 3 ratio of DCD Brook- *Disper- ppm free Example to one mole offield pH sion of formal- # formaldehyde Viscosity (5%) samples dehyde***62 3.988 214 8.32 0.717 103 63 3.988 48 88 Adjusted Ex #63 0.960***90 Ex #64 adjusted 119 8.22 0.860 148 with DMSO and Free DCD 64 2.5***91 Ex #65 adjusted 173 8.22 0.586 198 with DMSO and Free DCD 65 1.5**67 3.85 320 8.6 4.800 53 68 3.85 2.452 54 69 3.75 354 7.1 2.877 59**71 3.75 2.181 206 72 3.75 330 7.05 3.615 490 **73 2.2 adjusted insitu203 8.11 2.336 118 with free DCD 76 3.5 275 7.17 1.685 66 78 2 820 7.122.988 603 79 1.2 4780 7.09 0.700 180 82 3.5 275 7.15 3.920 41 83 3.5 3037.25 1.070 21 *grams of sample in 100 grams of Distilled Water (BarelyTranslucent in Appearance) **No acid catalyst charged ***sample containstriethanolamine

Most of the viscosity, pH and free formaldehyde data in Chart 3 arewithin expected ranges. However, some of the examples required furtherdilution to test dispersibility. Most of the above samples that did notneed dilution contain 42-46% polymer bound and free DCD. One example(e.g., example #63) required additional dilution to achieve a total DCDwith DMSO of 43-44%. Similarly, examples #90 and #91 represent adjustingexamples #64 and #65 to achieve a total DCD with DMSO of 43-44%, andalso achieved a ratio of polymer bound to free DCD ratios close to the52:48 of other examples.

It was expected that examples produced with similar molar ratios wouldhave similar dispersibility in water. It was also expected that waterdispersibility would decrease as the DCD to formaldehyde ratio decreasedwhich would result in an increase in polymer bound to free DCD ratio.Comparing the water dispersibility of examples 62 and 88 to examples 67and 68 did not support this expectation. Without being bound by theory,it is believed that the variation in solubility is related to the cyanogroup's presence as well as the distribution of polymer molecular weight(i.e., if more of the higher molecular species are present, the watersolubility is diminished). Reaction parameters such as catalyst versusnon-catalyst, the temperature at which the catalyst is charged, the timeand temperatures of the process conditions, the speed of removal ofwater either from the catalyst charge or from the by-product, water fromthe second reaction and the % of a NAPAOL in the reaction compositionare believed to be the conditions that influence water solubility.

Example 104

To determine the percent retention of the cyano group present in theexamples, an UV analytical procedure was ran in which a calculatedconcentration of total (polymer found and free) DCD for a number ofexamples was performed and a dilution of the examples were performed toreach a calculated concentration of total DCD of 8.7 ppm using aisopropanol/water solvent system.

Procedure:

-   -   1) A UV spectrophotometer, DU Beckman 640, was utilized to        determine the absorbance at specific UV wavelength of a diluted        sample that was contained in a 10 mm Quartz Cuvette    -   2) A blank was prepared that included water, propanol and NAPAOL        in the amounts present in the dilution of an example to 8.7 ppm        of total DCD.    -   3) A standard curve was plotted for UV absorbance for known        concentrations of DCD solutions of 8.7 ppm, 8.4 ppm, 8.0 ppm and        7.6 ppm representing respectively 43.5%, 42%, 40% and 38% DCD in        solution. FIG. 1 is the plot of DCD concentration versus UV        absorbance @ 211-216 nm.    -   4) The calculated concentration of examples was adjusted to a        43.5% level during the dilution process as shown in Chart 4:

CHART 4 Dil 1 Dil 2 Dil 3 Dil 4 Calculated Weight Total Total TotalExample total of DCD DCD DCD # DCD Example conc conc Conc 62 43.50% 5.000.2175 0.0004350 0.0000087 88   42% 5.18 0.2175 0.0004350 0.0000087 9042.42% 5.13 0.2175 0.0004350 0.0000087 91 42.42% 5.13 0.2175 0.00043500.0000087 67 43.91% 4.95 0.2175 0.0004350 0.0000087 68 44.94% 4.840.2175 0.0004350 0.0000087 69 44.76% 4.86 0.2175 0.0004350 0.0000087 7145.70% 4.76 0.2175 0.0004350 0.0000087 72 46.39% 4.69 0.2175 0.00043500.0000087 73 42.13% 5.16 0.2175 0.0004350 0.0000087 76 43.33% 5.020.2175 0.0004350 0.0000087 78 46.62% 4.67 0.2175 0.0004350 0.0000087 8245.80% 4.75 0.2175 0.0004350 0.0000087 83 45.80% 4.75 0.2175 0.00043500.0000087 Dil-1: weight of example in 45 grams of 50/50 IPA/Water toyield concentration of total DCD of 4.35% Dil-2: 5 grams of Dil 7, & 45grams 50/50 IPA/Water Dil-3: 50 grams Dil 2/450 Water Dil-4: 2 gm Dil3/100 mls

Each sample dilution was placed in the Beckman DU 640 Spectrophotomerand read and recorded 4 times at UV wavelengths of 211-216 nm. Chart 5shows the average of the three highest UV absorbance readings at 211-216nm and the resulting sample's absorbance is compared to theconcentration curve of the standard for DCD to estimate the sample's %total DCD.

CHART 5 estimated Average of Total UV DCD Estimated Example Absorbanceversus % cyano- # Readings standard retained Standard 1.467 43.50% 621.395 41.80% 96.09% 88 1.334 40.55% 93.22% 90 1.305 39.95% 91.84% 911.278 39.40% 90.57% 67 1.365 41.20% 94.71% 68 1.313 40.15% 92.30% 691.343 40.80% 93.79% 71 1.331 40.60% 93.33% 72 1.316 40.25% 92.53% 731.378 41.50% 95.40% 76 1.400 42.05% 96.67% 78 1.331 40.50% 93.10% 821.426 42.50% 97.70% 83 1.281 39.50% 90.80%

Comparison of the data from example 62 and example 88 shows asignificant drop in absorbance of example 88 indicating a loss ofcyano-function. Examination of the reaction conditions for both examplesreveals that even though example 62 was heated to 118° C., the methanesulfonic acid(MSA)/70% catalyst was charged at 42° C., whereas thereaction product for example 88 (example 63) was only heated to 95° C.,the MSA/70% catalyst was charged at 85° C. Without being bound bytheory, it is believed that the time, the temperature of the contents ofthe reaction vessel, the temperature at which the catalyst is introducedand the presence or absence of water have a major impact oncyano-function loss.

Examples 90, 91 and 73 are examples of low ratio DCD:Formaldehyde wherethe final ratio of polymer bound and free DCD are adjusted by the postreaction addition of free DCD. Examples 90 and 91 have low absorbancereadings while example 73 has higher absorbance readings. Examples 90and 91 were based on the reaction product of examples 64 and 65respectively where the MSA/70% was charged at 85° C. and the reactionwas heated to 110° C., removal of water was at the end of the reactionphase and the % composition of DMSO was around 45% during the reaction.Example 73 was at approximately 65% DMSO during the reaction phase andthe MSA/70% was charged at 70° C. and the extra DCD was charged and thereactor placed under vacuum to remove the water by-product during thesecond reaction.

Examples 76, 82 and 83 are very similar in formulation and in processwith the exception that example 76 has the catalyst MSA/70 charged tothe reaction vessel at 80° C. while Example 82 utilizes the catalystpTSA/100% and the catalyst is charged to the reaction vessel at 38° C.Without being bound by theory, it is believed that the catalyst MSA/70contains some water, which degrades the cyano group. In comparison thecatalyst pTSA/100% is substantially free of water and consequently doesnot degrade the available cyano groups. This theory is further supportedby Example 83, which is example 82 with approximately 9-10% distilledwater added. In both examples 82 and 83, the water is stripped out.

The UV absorption results show that utilizing a non-water containingcatalyst that is charged at a low temperature results in higherabsorption readings. Example 83 shows that the presence of water duringreaction temperature results in lower UV absorption numbers.

Example 105

35 grams of DMSO was warmed to 45° C., then 15 grams of2-chloro-6-trichloromethyl)pyridine was charged and the composition wasmixed for 45 minutes until mixture was clear. 50 grams of Example 76 wascharge and the new composition was mixed for 1 hour. The product waspackaged. A check of the sample after 6 weeks of storage found it wasstill clear. Another sample of the composition was placed in an oven @50° C. and after three days was found to be stable.

Example 106

49.44 grams of example 76 were charged to reaction flask and placedunder agitation. The pH was adjusted to 9.6 with NaOCH₃/25% and agitatedfor 15 minutes. 5.56 grams of paraformaldehyde were charged andcomposition was heated to 70° C. and held for five hours and then heatedto 80° C. for 30 minutes. The composition was then cooled to 40° C. andheld under agitation. The appearance of the composition was slightlyhazy.

Example 107

To reactor 285 grams of molten urea was charged and then the vessel wasdeoxygenate 3 times by evacuating with vacuum and sparged with ammoniagas to slow degradation of urea under molten conditions. All spargingtubes and themometers had to be removed to prevent breakage and an astainless steel agitator shaft and blade were utilized due to thedifficulty in agitating granular urea. The urea was heated withagitation until molten and then the thermometer and sparge tube werere-inserted. The temperature reading was 148.3° C. and the molten ureawas again sparged with ammonia gas. 15 grams of Example 106 were slowlycharged to the molten urea while controlling the exotherm with chargerate and removing heating mantel. After 30 minutes, example 106 chargewas completed and the composition was agitated at 145-155° C. under anammonia atmosphere to 15 minutes. The composition had a slight hazyappearance and was then poured on a dimpled steel sheet, cooled andpackaged for further evaluation.

Example 108

15.17 grams of dicyandiamide were charged to reaction flask thatcontained 29.0 grams of DMSO under agitation. The composition was heatedto 80° C. and mixed at 80° C. until the dicyandiamide had dissolved. Thecomposition was then cooled to 45° C. where 10.83 grams ofparaformaldehyde were charged and mixed until a consistent slurry wasformed.

Example 109

To reactor 285 grams of molten urea was charged and then the vessel wasdeoxygenate 3 times by evacuating with vacuum and sparged with ammoniagas to slow degradation of urea under molten conditions. All spargingtubes and themometers had to be removed to prevent breakage and an astainless steel agitator shaft and blade were utilized due to thedifficulty in agitating granular urea. The urea was heated withagitation until molten and then the thermometer and sparge tube werere-inserted. The temperature reading was 148.3° C. and the molten ureawas again sparged with ammonia gas. 15 grams of Example 108 were slowlycharged to the molten urea while controlling the exotherm with chargerate and removing heating mantel. After 30 minutes, example 106 chargewas completed and the composition was agitated at 145-155° C. under anammonia atmosphere to 15 minutes. The composition showed a slight milkyappearance and was then poured on a dimpled steel sheet, cooled andpackaged for further evaluation.

Example 110

49.48 grams of example 79 and 20 grams of DMSO were charged to reactionflask and placed under agitation. The pH was adjusted to 9.4 withNaOCH₃/25% and agitated for 15 minutes. 5.52 grams of paraformaldehydewere charged and composition was heated to 70° C. and held for fivehours and then heated to 80° C. for 30 minutes. The composition was thencooled to 40° C. and held under agitation. The appearance of thecomposition was slightly hazier than example 106 and slightly viscous.

Example 111

To reactor 285 grams of molten urea was charged and then the vessel wasdeoxygenate 3 times by evacuating with vacuum and sparged with ammoniagas to slow degradation of urea under molten conditions. All spargingtubes and themometers had to be removed to prevent breakage and an astainless steel agitator shaft and blade were utilized due to thedifficulty in agitating granular urea. The urea was heated withagitation until molten and then the thermometer and sparge tube werere-inserted. The temperature reading was 148.3° C. and the molten ureawas again sparged with ammonia gas. 15 grams of Example 110 were heatedto 65° C. were slowly charged to the molten urea while controlling theexotherm with charge rate and removing heating mantel. After 30 minutes,example 106 charge was completed and the composition was agitated at145-155° C. under an ammonia atmosphere to 15 minutes. The compositionhad a slight hazier appearance compared to example 107 and was thenpoured on a dimpled steel sheet, cooled and packaged for furtherevaluation.

Example 112

A number of the examples were tested for nitrification inhibition onurea. The experimental samples were applied to urea using standardoverhead mixer with an anchor agitator. The amount of the sample tocharge was determined by the specific gravity of the sample times thevolumetric treatment level. For example:

-   Determining the amount of Example 76 to be charged at a rate of 3    quarts/ton of urea:    -   Specific gravity=1.163 gm/ml=9.68 lb/gal    -   At an application level of 3 quart/ton of urea=7.26 lbs of        Example 76/2000 lbs of urea    -   The application level would be 0.363% of Example 76

The 200 grams of urea was placed in a vessel, agitation was set so notto sling the urea out of the vessel and the calculated amount of theexperimental sample was dripped onto the agitating urea. Aftercompleting the sample addition, the urea was agitated for an additionalminute to insure uniform coverage.

The examples 62, 68, 73, 75 and 76 were adjusted to a calculated DCDlevel of 30% with DMSO and FD&C Blue #1 Food Color as shown in the Chart6:

CHART 6 DCD/ Ex-62/ Ex-68/ Ex-73/ Ex-75/ Ex-76/ Ingredients 30% 30% 30%30% 30% 30% DCD-34% 88.3% DMSO 10.5% 29.73 31.94 27.54 18.49 27.27 FD&C 1.2% 1.3 1.3 1.3 1.3 1.3 Blue #1 Example 68.97 62 Example 66.76 68Example 71.16 73 Example 80.21 75 Example 71.43 76

Each sample was applied to 200 grams of urea at a 3 quart/tonapplication rate.

Example 113:

In 143.5 cubic inch plastic containers with a hole in the side largeenough for a Drager tube to be safely inserted, 200 grams of West TexasSoil (Estacado Clay Loam) with a moisture content of 37% and 75 grams ofdistilled water were added and mixed. The surface area of the soil wascalculated to 47.8 sq inches. Exactly 1.1 grams of each urea sample wasadded to the surface of the soil and the plastic container and its holewere sealed. The headspace of each sealed container was analyzed for ppmammonia by using a handheld Drager pump attached to the Drager tubewhich was inserted into the plastic container's hole and the pump wasmanually engaged 10 times. The readings were then recorded. Regardlessof whether a reading of ppm ammonia was made each day on the samples'containers, each container was opened and fanned to insure that thereading of ammonia build up was for a 24 hour cycle. The results of testare in the Chart 7 which provides the data for graph listed as “FIG. 6”((good nitrification inhibition results in high ammonia ppm readings):

CHART 7 Ammonia Generated (ppm) Sample Days ID on 5 6 10 11 13 17 20 2427 Urea (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) DCD/30%300 625 500 520 600 550 490 380 300 Example 275 610 600 610 750 700 560875 700 73/30% Example 550 600 615 600 725 675 620 690 600 76/30% Urea(untreated) 50 100 420 540 700 450 420 350 200

A nitrate concentration analysis was performed on the soil after 30 daysusing a standard colormetric method in which a 1M KCl extraction of thesoil is performed and is then passed through a copperized cadmiumcolumn. After diazotizing with sulfanilamide and followed by couplingwith N-(1-naphthyl)ethylenediamine dihydrochloride, a color intensity isread at 520 nm. The Chart 8 contains the results of the analysis (goodnitrification inhibition results in low nitrate ppm readings):

CHART 8 Sample ID on ppm of urea nitrate DCD/30% 9 Example 73/30% <1Example 76/30% <1 Urea (untreated) 81

Example 73 and Example 76 were combinations of DCD-formaldehyde oligomerwith free DCD. While both were similar in composition, the free DCD wasadded to Example 73 post reaction while the free DCD was present duringthe reaction in Example 76. Because of the composition of the reactantsin both examples, one would expect a broader oligomer/polymer molecularweight distribution in example 73 due to the 2.2:1 DCD to formaldehydemolar ratio while the excess DCD present in the reaction of example 76due to the 3.5:1 DCD to formaldehyde ratio would result in a higherpercentage of the methylene bis dicyandiamide oligomer. Results showedthat both examples out performed DCD by itself.

Example 114

In 66.1 cubic inch plastic containers with a hole in the side largeenough for a Drager tube to be safely inserted, 200 grams of West TexasSoil (Estacado Clay Loam) with a moisture content of 37% and 75 grams ofdistilled water were added and mixed. The surface area of the soil wascalculated to 33.1 sq inches. Exactly 0.75 grams of each urea sample wasadded to the surface of the soil and the plastic container and its holewere sealed. The headspace of each sealed container was analyzed for ppmammonia by using a handheld Drager pump attached to the Drager tubewhich was inserted into the plastic container's hole and the pump wasmanually engaged 10 times. The readings were then recorded. Regardlessof whether a reading of ppm ammonia was made each day on the samples'containers, each container was opened and fanned to insure that thereading of ammonia build up was for a 24 hour cycle. The results of testare in the Chart 9 below which provides the data for graph listed as“FIG. 7”:

CHART 9 Ammonia Generated (ppm) Impact of conserving cyano group*Estimated Sample % cyano Days ID group 7 11 14 18 21 25 28 32 opn urearetained (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) Example 96.09%95 225 540 620 580 290 210 62/30% Example 92.30% 45 180 300 560 500 190150 68/30% Example 96.67% 50 200 580 670 640 540 290 140 76/30% *FromExample # 104/Chart #5

Example 62, Example 68 and Example 76 were combinations ofDCD-formaldehyde oligomer with free DCD. All three were similar incomposition and the free DCD was present during the reaction in in allthree examples. Because of the composition of the reactants in the threeexamples are close, one would expect similar nitrification inhibitionproperties. However, the lower cyano group retention negatively impactedthe nitrification inhibition of example 68.

Example 115

In 66.1 cubic inch plastic containers with a hole in the side largeenough for a Drager tube to be safely inserted, 200 grams of West TexasSoil (Estacado Clay Loam) with a moisture content of 37% and 75 grams ofdistilled water were added and mixed. The surface area of the soil wascalculated to 33.1 sq inches. Exactly 0.75 grams of each urea sample wasadded to the surface of the soil and the plastic container and its holewere sealed. The headspace of each sealed container was analyzed for ppmammonia by using a handheld Drager pump attached to the Drager tubewhich was inserted into the plastic container's hole and the pump wasmanually engaged 10 times. The readings were then recorded. Regardlessof whether a reading of ppm ammonia was made each day on the samples'containers, each container was opened and fanned to insure that thereading of ammonia build up was for a 24 hour cycle. The results of testare in the Chart 10 below which provides the data for graph listed as“FIG. 8”:

CHART 10 Ammonia Generated (ppm) DCD-Formaldehyde oligomer versus DCDonly Days Sample 7 11 14 18 21 25 28 32 ID (ppm) (ppm) (ppm) (ppm) (ppm)(ppm) (ppm) (ppm) DCD/30% 100 210 510 800 690 300 200 100 Example 50 200600 860 620 550 480 330 75/30% urea 45 60 100 275 500 490 330 170

Example 75 is DCD-formaldehyde oligomer without the addition of freeDCD. The composition of the reactants in example 75 is 2.2:1 molar ratioof DCD to formaldehyde. That molar ratio would lead one would expectsome level of unreacted DCD to be present. While both DCD and Example 75performed equivalently, at 25 days, the DCD performance drops off moresubstantially versus Example 75. The results show that theDCD-formaldehyde oligomers do have improved longevity versus DCD only.

Example 116

Analysis of the Dicyandiamide-Formaldehyde Reaction Products UtilizingDMSO as the NAPAOL by FTIR.

The reaction of formaldehyde with the amine groups of dicyandiamideresults in a simple composition when the molar ratio of DCD toformaldehyde is1.2:1 to 4.0:1. Under reaction parameters established inpreparation of many of the examples yield a final product that containsDCD-formaldehyde adducts, unreacted DCD, DMSO and a trace offormaldehyde (<200 ppm). The DCD-formaldehyde adduct is DCD unitscrosslinked through a methylene bridge between two DCD amine groups.

(2)DCD-NH₂+(1)CH₂O→DCD-HN—CH2-NH-DCD+H₂O

Although there is no major function group changes during the reaction,there is a modification of the amine groups and the introduction ofN—CH₂—N group. Regions of interest are 3500-3100 cm⁻¹ (primary aminestretching and secondary amine stretching) and 1130 cm⁻¹ (N—CH₂—Nvibration).

Chart 11 list the examples and their molar ratios of DCD to formaldehyde

CHART 11 Molar ratio of DCD to FIG. # FTIR Scan ID Formaldehyde #5 DCDNA #2 Example 76 3.5:1 #3 Example 74 2.2:1 #4 Example 79 1.2:1

Examination of the FTIRs in FIGS. 2-4 shows the deformation of the peaksin the region of 3400-3100 cm⁻¹ (N—H stretching) as changes in the molarratios increases the weight percent of formaldehyde in the reactionresulting in the conversion of more primary amine to secondary amines.

In examination of FIG. 5 (DCD), there is no peak in the 1130-1135 cm-1region. FIG. 2 (Example 76) shows a small peak at 1132 cm-1. The peak at1132 cm-1 (N—C—N stretching) becomes more pronounced as the weight % ofmethylene bridges increases due to the increase in the weight percent offormaldehyde in the reaction. The examination of the peak at 1130-1135cm-1 in FIG. 4 shows a more intensity versus FIG. 2

Comparing FIG. 5(DCD) to FIG. 2-4 shows that the DCD has been modifiedand that a DCD-formaldehyde oligomer/polymer has been formed.

The presence of water degrades the available cyano groups. It should beclear that there are advantages to the instant invention when thereactions are performed in the absence of water. Using an aqueous mediumlimits applications to systems or processes not negatively impacted bythe presence of water. The present invention has the advantage of notrequiring other formaldehyde reactive constituents such urea and ammoniawhich are needed to impart water solubility to assist with thedicyandiamide (DCD) since DCD has a limited solubility in water ofapproximately 32 grams/liter at 20° C. The low DCD amounts in aqueoussolution result in slower reactivity and low concentrations of theresulting polymers and oligomers. Performing the reaction in the absenceof water does not generate the side products that result from thecomparable reactions that are done in the presence of water. This isbecause when the reactions are performed in the absence of water, theadditional components that are necessary when the reaction is performedin water are not present. For example, when the reaction is done inwater with urea and ammonia, the resulting composition of the reactionproduct is a mixture of the following undesirable by-products:triazonyl-formaldehyde-DCD adducts, a urea-formaldehyde-DCD adduct andthe desirable polymers and/or oligomers. When the reaction is performedin the presence of water, the composition of the formaldehyde reactionproduct comprises only about 0.1 to 10 wt. % of aDCD-formaldehyde-oligomer adduct based upon the weight of thenitrification inhibitor system. In contrast, when the reaction isperformed in the absence of water, as in the present invention, muchhigher amounts of DCD-formaldehyde-oligomer adduct is generated.

Moreover, as shown by the above examples, biologically active agents canbe added to the hydrophobic, biodegradable polymers that have beenproduced within the NOSDS, dimethyl sulfoxide and further can be addedto the hydrophobic, biodegradable polymers that have been producedwithin the NOSDS, dimethyl sulfoxide and further formulated with proticand aprotic solvents to produce products that slow the dissolution ofurea into water.

Example 117

Qualitative analysis by HPLC (High Pressure Liquid Chromatography) andMS (Mass Spectroscopy) were performed on example 76 and example 78utilizing Agilent Technologies Model 6520 QTOF for MS and AgilentTechnologies Model 1200 LS for HPLC with the following parameters:

-   -   Elution method: isocratic elution with 4% ammonium acetate        buffer (1 mM) and 96% acetonitrile (ACN)    -   Flow rate: 0.5 ml per minute    -   Time: 5 minutes    -   Injection: 1 μL    -   Column: HILIC Acquity BEH Amide column (2.1×50 mm, 1.7 μ)

FIG. 11 shows the chromatograph of example 78 while FIG. 12 shows the MSof the peaks in the chromatograph of example 78. The protonated moleculeof DCD with a m/z 85.051 and the sodiated adduct of DCD with an m/z107.033 were observed under electrospray ionization (ESI) conditions.The protonated form of the dimer (C₅H₈N₈) appears at m/z of 181.095 anda sodiated form at 203.076 and the protonated trimer (C₈H₁₂N₁₂) appearsat m/z of 277.138 under ESI conditions. However, no sodium adduct wasobserved for the trimer. More DCD-methylol structures at m/z of 115.0867and DCD-formaldehyde dimer-methylol structures at m/z of 211.1049 werealso observed in the MS of example 78 versus example 76. Without beingbound by theory, this is due to the higher ratio of formaldehyde to DCD.There are a number of unidentified small peaks within the MS, however,in ESI, different ions related to the analyte and solvent can be formed,so it is very difficult to identify all the masses in a spectrum andsome peaks that relate to other molecular fragments. For example, thetwo m/z's at 169.0832 and at 193.0944 represent fragments from thepolymer break at the methylene bridge of a tetramer. An intense response(peak) was also measured at an m/z of 124.0873. However this m/z is dueto ACN, under ESI conditions, forming a trimer. The trimer show up underthree peaks related to retention time of the chromatograph. This is dueto the sticky nature of these compounds causing them to reside in theQTOF for some time or sticking to the walls of the tubing.

The results from qualitative analysis are summarized in Table 12.

TABLE 12 Retention and m/z Data for DCD and Samples. Reten- ProtonatedStructure tion mass-to-charge DCD and DCD Sample source time(min) ratioformaldehyde structures DCD calibra- 0.76 85.0513 DCD tion standard 0.75107.0328 * DCD -Na Example 76 0.75 85.0513 DCD 1.42 181.0942 Dimer 2.24181.0946 Dimer 2.24 277.1386 Timer 2.94 277.1384 DCD Timer 2.94 115.0867DCD with methylol group 3.72 277.1390 Timer Example 78 0.75 85.0513 DCD1.43 181.0942 Dimer 1.43 115.0614 DCD with methylol group 1.43 211.1049Dimer with methylol group 2.26 181.0945 Dimer 2.26 277.1382 Timer 2.97115.0866 DCD with methylol group 2.97 277.1383 Timer 3.75 115.0865 DCDwith methylol group 3.75 277.1382 Timer • DCD-Na is not a protonatedstructure but a sodiated structure

TABLE 13 DAD peak areas from DAD and Mass Spec Sample Molecule DCDMonomer DCD Dimmer OCD Trimer Example 76 (Coded 17K13) 17K13 m/z 85.0513107.0327 181.0942 203.0764 277.1386 277.1384 277.139 EIC Area 7584378785355 4275011 1518747 434659 2241908 1291096 EIC Sum 8369733 57937583987563 % Area sum 46.16% 31.95% 21.88% Example 78 (Coded 18C14) 18C14m/z 85.0513 107.033 181.0942 203.0766 277.1386 277.1384 277.139 EIC Area6336128 744701 3469611 714232 306887 1237643 1191386 EIC Sum 70808294183849 2735925 % Area sum 50.58% 29.88% 19.54%

EIC (Extracted Ion Chromatogram) was obtained by extracting the TotalIon Chromatogram at a specific exact m/z value. The normalized Ratio ofDCD, Dimer and Trimer is obtained by dividing the area of the individualcomponents by the sum of those three components and multiplying theproduct by 100 as in the below Equation:

Normalized Ratio of DCD=100* (Area DCD/(Area DCD+Area Dimer+Area Trimer)

Because of the limits of the MS that was utilized, all otherDCD/formaldehyde oligomers with polymer/molecular weights greater than300 will not generate an m/z measurement.

Example 118

41.72 grams of Example 73 were blended with 75 grams of apolysuccinimide-(PSI) (polymer weight 3000-5000 grams/mole) and grams ofDMSO at 60° C. and mix until the PSI had disdolved. The example wascooled and package. Sample appearance was red and clear.

Example 119

35 grams of a polysuccinimide-(PSI) (polymer weight 3000-5000grams/mole) neutralized with ammonia in 35 grams of DMSO was added toExample 73 and mixed until homogeneous. The sample was clear and red incolor.

Example 120

14 grams of a low moisture dipotassium zinc ethylene diaminetetraacetate dispersed in ethylene glycol wherein the dipotassium zincethylene diamine tetraacetate weight percent was 47% was added toExample 78 that be heated to 40 C, mixed until homogeneous, cooled andpackaged. The appearance was clear with a slight haze. (Note the Example78 had a slight haze). This example contains 1% elemental zinc.

Example 121

55 grams of DMSO and 40 grams of Example 119 and 5 grams of N-(n-butyl)thiophosphoric triamide were mixed at 40 C until homogeneous, cooled andthen packaged, Appearance was clear and the color was red.

Example 122

10 grams of a (hexylaminomethylene, aminomethylene) phosphinic acid(C₈H₂₀N₂0₂P) potassium salt dispersed in ethylene glycol was added toexample 119, mix at 40 C until homogeneous, cooled and then packaged.Appearance was clear and the color was red.

In an embodiment, the NOSDS not only provides the solvating property forthe hydrophobic, biodegradable polymer but also serves as the deliverysystem for the hydrophobic, biodegradable polymers to the surface offertilizer granules. In a variation, the NOSDS provides solvatingproperties to one of more biologically active agents selected from thegroup consisting of urease inhibitors, nitrification inhibitor(s),pesticide(s), herbicide(s), fungicides(s), and insecticide(s).

In an embodiment, incorporating within the NOSDS one of morebiologically active agents selected from the group consisting of ureaseinhibitors, nitrification inhibitor(s), pesticide(s), herbicide(s),fungicides(s), and insecticide(s) with the biodegradable, hydrophobicpolymers that are the reaction product of aldehyde(s) and nitrogencontaining compounds will result in lower dissolution of thesebiologically active agents that are encapsulated within the hydrophobicfilm thereby improving performance by increasing the length of timethese biologically active agents are available.

In an embodiment, the composition of the biodegradable, hydrophobicpolymers that are the reaction product of aldehyde(s) and nitrogencontaining compounds dispersed within a NOSDS can further comprise oneor more urease inhibitors selected from the group consisting ofaliphatic phosphoric triamide, phosphoramides and N-alkyl thiophosphorictriamides, (aminomethyl)phosphinic acids and their salts and aminomethyl(alkylaminomethyl)phosphinic acids and their salts. In a variation theurease inhibitor is N-(n-butyl) thiophosphoric triamide.

In an embodiment, the composition of the biodegradable, hydrophobicpolymers that are the reaction product of aldehyde(s) and nitrogencontaining compounds dispersed within a NOSDS can further comprise oneor more nitrification inhibitors selected from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4-6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD),thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate,dimethylpyrazole organic and inorganic salts and2-amino-4-chloro-6-methylpyrimidine In a variation the nitrificationinhibitor is dicyandiamide.

In an embodiment the composition of the biodegradable, hydrophobicpolymers that are the reaction product of aldehyde(s) and nitrogencontaining compounds dispersed within a NOSDS can further comprise oneor more nitrification inhibitors selected from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4-6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD),thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate,dimethylpyrazole organic and inorganic salts and2-amino-4-chloro-6-methylpyrimidine and one or more urease inhibitorsselected from the group consisting of aliphatic phosphoric triamide,phosphoramides and N-alkyl thiophosphoric triamides,(aminomethyl)phosphinic acids and their salts and aminomethyl(alkylaminomethyl) phosphinic acids and their salts.

In an embodiment, one can coat a granule of treated urea with thebiodegradable, hydrophobic polymers that are the reaction product ofaldehyde(s) and nitrogen containing compounds dispersed within a NOSDS.Treated urea is defined as a urea composition comprising urea and abiologically active agent added either through a coating application oradded to the urea during the urea production process either in the meltportion or deposited to the urea during the formation of the ureagranule when the urea is still hot. In a variation, the treated urea canbe mixed with other fertilizer components and then coated with thebiodegradable, hydrophobic polymers that are the reaction product ofaldehyde(s) and nitrogen containing compounds. This will impart slowerdissolution of these fertilizer components and urea into water becausethey have been encapsulated within the hydrophobic film, therebyimproving performance by increasing the length of time the fertilizer isavailable.

In one embodiment, the composition of the liquid formulation comprisesone or more biodegradable, hydrophobic polymers that are the reactionproduct of aldehyde(s) and nitrogen containing compounds and NOSDS. Thiscomposition is used to coat a dry granular urea, which is then appliedto cropland and turf The hydrophobic coating makes the urea moreeffective in providing nutrients for plant growth over an extendedperiod of time. In a variation, the composition of the liquidformulation comprising urea and the biodegradable, hydrophobic polymersthat are the reaction product of aldehyde(s) and nitrogen containingcompounds and NOSDS further comprise one of more biologically activeagents selected from the group consisting of urease inhibitors,nitrification inhibitor(s), pesticide(s), herbicide(s), fungicides(s),and insecticide(s) which when applied to cropland and turf makes theurea more effective in providing nutrients for plant growth over anextended period of time.

In an embodiment, biodegradable, hydrophobic polymers that are thereaction product of aldehyde(s) and nitrogen containing compounds can beproduced by reacting the aldehyde(s) with the nitrogen containingcompounds within the NOSDS. In a variation, the NOSDS comprises dimethylsulfoxide.

In an embodiment, dicyandiamide can be dispersed within dimethylsulfoxide and then reacted with paraformaldehyde in a molar ratio of 3-4moles of dicyandiamide to one reactive unit of paraformaldehyde. Thisresults in a composition comprised of dicyandiamide, that has reacted aswell as some unreacted dicyandiamide. The composition unexpectedlycontains DCD that is present at 35-60% by weight that will survive 3freeze/thaw cycles (that is, the DCD does not crash out of solution).This is an unexpected result since the compositional percentage ofdicyandiamide in a solution with dimethyl sulfoxide at a temperature ofless than 35° C. was thought to not be able to exceed 35% by weight. Ina variation, such a composition can also be applied to urea as anitrification inhibitor providing extended nitrification inhibition dueto the slow release of DCD into a plant growth media. In anothervariation, the composition can be added to an anhydrous ammoniaformulation for sub-surface applications by injection of the anhydrousammonia formula directly into the soil.

In an embodiment, the composition of the active hydrophobic coatingagent comprises 5-60% of the biodegradable, hydrophobic polymers thatare the reaction product of aldehyde(s) and nitrogen containingcompounds and 95-40% of NOSDS. In a variation, the composition canfurther comprise 1 to 45% of biologically active agents.

In an embodiment, the method to make biodegradable, hydrophobic polymersthat are the reaction product of aldehyde(s) and nitrogen containingcompounds is a) dissolve the nitrogen containing compounds in an aproticsolvent at temperatures in the range of 30-110° C., then cool to 40-60°C. and insure that pH is in the range of 8-10, b) slowly add thealdehyde and allow the exotherm to be controlled either through chargerate or removing the heat of reaction through a cooling median, c)slowly heat the composition to 70-90° C. and hold for a period of time,d) cool the composition to 40-70° C., and slowly charge enough of anacid catalyst to drop the pH to 5-6.5 and let mix for an extended periodof time to control the exotherm, e) slowly heat the composition to90-115° C., f) after holding for a period of time, one can elect toplace the batch under a vacuum to assist in removing water by-products,driving the reaction to more completion and removing any unreactedaldehyde and then cooling the batch. In a variation, one can chargeprotic and aprotic solvents to improve flow properties and storagestability. In another variation, one can charge a low molecular weightalcohol to improve and control the reaction. One can also cap unreactedmethylene hydroxides through charging low molecular weight alcohols.

In an embodiment the % composition of the biodegradable, hydrophobicpolymers that are the reaction product of aldehyde(s) and nitrogencontaining compounds is stoichiometrically set to insure that there isno free formaldehyde or unreacted methylol groups remaining in the finalproduct. In a variation, residual methylol groups can be capped by theaddition of a low molecular weight alcohol such as but not limited tomethanol, ethanol, propanol and butanol. In another variation, due tothe penetration of urea by dimethyl sulfoxide, the alcohol cappedmethylol groups can be further reacted onto and with the surface of theurea utilizing temperature and catalysts known to those skilled in theart of reacting alcohol capped methylol groups, further improving thehydrophobic properties of the coating.

In an embodiment, the minimum application level of the liquidcomposition (of the biodegradable, hydrophobic polymers) is 3 quartsapplied to one ton of urea. This mix provides extended time for plantsto receive the nutrients from the treated fertilizer. In a variation,the liquid composition that is applied at a level of 3 quarts/ton ofurea further comprises biologically active agents.

In an embodiment, the liquid composition of the biodegradable,hydrophobic polymers that are the reaction product of aldehyde(s) andnitrogen containing compounds dispersed within a NOSDS can furthercomprise monomers such as but not limited to tetramethoxy glycoluril orhexamethoxymethylmelamine. These additional monomers impart furthercrosslinking of the polymer to the surface of urea due to thepenetration of urea by dimethyl sulfoxide. In a variation, Example 18 isa ready to use crosslinker dispersed in dimethyl sulfoxide that can bereadily incorporated into the liquid composition.

In an embodiment, the water resistance of fertilizer coated with theliquid composition of the biodegradable, hydrophobic polymers that arethe reaction product of aldehyde(s) and nitrogen containing compoundsdispersed within a NOSDS can improve with time and with heat.

In an embodiment, a water resistant fertilizer is comprised of urea andthe liquid composition of the biodegradable, hydrophobic polymers thatare the reaction product of aldehyde(s) and nitrogen containingcompounds dispersed within a NOSDS. In a variation the water resistantfertilizer is further comprised of one or more biologically activeagents selected from the group consisting of urease inhibitors,nitrification inhibitor(s), pesticide(s), herbicide(s), fungicides(s),insecticide(s), flow modifiers and methylol capped monomers that are thereaction product of aldehyde(s) and nitrogen containing compounds. In avariation the flow modifier is a hydrophobic silica. In anothervariation, the one or more methylol capped monomers that are thereaction product of aldehyde(s) and nitrogen containing compounds areselected from the group consisting of tetramethoxy glycoluril,Tetra(methoxymethyl) urea, di(methoxymethyl) urea andhexamethoxymethylmelamine.

In an embodiment, the present invention relates to a compositioncomprising one or more biodegradable hydrophobic polymers of a molecularweight range of 50-200,000 Daltons and a Non-aqueous Organo SolventDelivery System (NOSDS), wherein said composition is a stable dispersionideally suited to coat man-made and/or natural fertilizer components,wherein the biodegradable, hydrophobic polymers comprise the reactionproducts of aldehyde(s) and nitrogen containing compounds and whereinthe NOSDS is comprised of a) one or more protic solvents selected fromthe group consisting of: 1) an alcohol from the family of C₁₋₁₀alkanols, 2) one or more polyols selected from the group consisting oftrimethylol propane, trimethylol ethane, pentaerythritol, sorbitol,sorbitan, glucose, fructose, galactose, and glycerin, 3) one or morepoly(C₁₋₁₀ alkylene) glycols represented by the structure:

H(C_(t)H_(u))_(v)OH

t is an integer: 1-10

u is an integer: 2-20

and v is an integer: 1-20,

4) one or more alkylene glycols selected from the group consisting ofethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, andbutylene glycol, 5) isopropylidene glycerol 6) one or more alkyleneglycol alkyl ethers selected from the group represented by thestructure:

-   -   Where R¹ is: CH₃, C₂H₅, C₃H₇ or C₄H₉    -   Where R² is: H or the structure

-   -   where R³ is: H or CH₃    -   where R⁴ is H and CH₃    -   and f is an integer between 1 and 15        7) one or more alkyl lactates selected from the group consisting        of ethyl, propyl and butyl lactate, 8) one or more alkanolamines        selected from the group represented by the structure:

-   -   where R⁵ is: C₂H₄OR⁸ or C₃H₆OH    -   where R⁶ is: H, C₂H₄OR⁸ or C₃H₆OH    -   where R⁷ is: H, C₂H₄OR⁸ or C₃H₆OH    -   where R⁸ is: (C₂H₄O)_(g)H    -   and g is an integer between 1-10        and 9) glycerol carbonate,

b) and one or more aprotic solvents selected from the group consistingof 1) dimethyl sulfoxide and 2) dialkyl, diaryl, or alkylarylsulfoxide(s) having the formula:

R₉S(O)_(x)R₁₀

-   -   wherein R₉ and R₁₀ are each independently a C₁₆ alkylene group,        an aryl group, or    -   C₁₋₃alkylenearyl group, or R₉ and R₁₀ with the sulfur to which        they are attached form a 4 to 8 membered ring wherein R₉ and R₁₀        together are a C₁₋₆ alkylene group which optionally contains one        or more atoms selected from the group consisting of O, S, Se,        Te, N, and P in the ring and x is 1 or 2,        3) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate, 4) one or more polyols capped with acetate        or formate wherein the polyol portion selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and glycerin, 5) one or more        alkylene glycol alkyl ethers acetates selected from the group        consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and tripropylene        glycol butyl ether acetate and, 6) isophorone, 7) one or more        diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate, 8) dimethylacetamide, 9)        dimethylformamide, 10) dimethyl-2-imidazolidinone, 11)        1-Methyl-2-pyrrolidone, 12) hexamethylphosphoramide, 13)        1,2-dimethyloxyethane, 14) 2-methoxyethyl ether,        15)cyclohexylpyrrolidone and 16) limonene.

In an embodiment, the aldehyde(s) portion of biodegradable, hydrophobicpolymers resulting from the reaction products of aldehyde(s) andnitrogen containing compounds comprise one or more aldehyde(s) selectedfrom the group represented by the structure:

-   -   where Q is: O, S    -   where R¹¹ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —CH═CH₂,        —C₄H₃O, —C₇H₇, —C₆H₅, —C₆H₁₁, CHO, C₂H₃O, C₃H₅O, C₄H₇O, C₇H₅O or        —R¹²O₂R¹³,    -   where R¹² is: —C, —C₂H₂, —C₃H₄, —C₄H₆, —C₅H₈, —C₆H₁₀    -   where R¹³ is: —H, CH₃, C₂H₃, C₃H₇, C₄H₉.

In an embodiment, the nitrogen containing compounds portion ofbiodegradable, hydrophobic polymers resulting from the reaction productsof aldehyde(s) and nitrogen containing compounds comprise one or morenitrogen containing compounds selected from the group represented by thestructures:

-   -   where A is: O, S    -   where R¹⁴is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(a)NH₂    -   where a is an integer: 1-10    -   where R¹⁵is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(b)NH₂    -   where b is an integer: 1-10    -   where R¹⁶is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(c)NH₂    -   where c is an integer: 1-10    -   where R¹⁷ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(d)NH₂    -   where d is an integer: 1-10,

and their tautomeric forms,

-   -   where X₁ is: —NHR¹⁸, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   where R¹⁸ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂, C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅    -   where X₂ is: —NHR¹⁹, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   where R¹⁹ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂, —C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅    -   where X₃ is: —NHR²⁰, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   where R²⁰ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂, —C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅        and d)    -   NH₂CO—R²¹    -   where R²¹ is an alkyl radical CH₃ to —C₁₇H₃₅.

In an embodiment, the composition of the biodegradable hydrophobicpolymers comprise the reaction products of aldehyde(s) and nitrogencontaining compounds which comprise one or more aldehydes selected fromthe group consisting of:

-   -   methanal, ethanal, propanal, butanal, pentanal, hexanal,        methylethanal, methylpropanal, methylbutanal,        phenylacetaldehyde, benzaldehyde, 2-propenal, 3-oxopropanoic,        2-methyl-3-oxopropanoic acid, 4-oxobutanoic acid, oxoacetic        acid, 5-oxopentanoic acid, 6-oxohexanoic acid, 2-oxopropanal,        cyclohexanal, furfural, methyl esters of 3-oxopropanoic,        2-methyl-3-oxopropanoic acid, 4-oxobutanoic acid, oxoacetic        acid, 5-oxopentanoic acid and 6-oxohexanoic acid, ethandial,        1,3-propanedial, butanedial, pentanedial, phthalaldehyde or        methanethial.

In an embodiment, the composition of the biodegradable hydrophobicpolymers comprise the reaction products of aldehyde(s) and nitrogencontaining compounds which comprise one or more nitrogen containingcompounds comprise selected from the group consisting of:

-   -   urea, biuret, polyurea, thiourea, methylurea, dimethylurea,        ethylurea, diethylurea, propylurea, dipropylurea, butylurea,        dibutylurea, phenylurea, diphenyl urea, pentylurea,        dipentylurea, hexyl urea, dihexyl urea, methylthiourea,        dimethylthiourea, ethylthiourea, diethylthiourea,        propylthiourea, diporpylthiourea, butylthiourea,        dibutylthiourea, pentylthiourea, dipentylthiourea,        hexylthiourea, dihexylthiourea, phenylthiourea,        diphenylthiourea, cyanamide, dicyandiamide, tricyantriamide,        melamine, hydroxy oxypentyl melamine, methylaminomelamine,        dimethylaminopropylmelamine, 1,3,5-Triazine-2,4,6 triamine,        2,4-diamino-1,3,5-triazine, 2,4-diol-6-Amino-1,3,5-triazine,        2,4-Diamino-6-hydroxy-1,3,5-triazine,        2-Butylamino-4,6-diamino-1,3,5-triazine,        2,4-Diamino-6-methyl-1,3,5-triazine,        2,4-Diamino-6-dimethylamino-1,3,5-triazine,        2-Amino-1,3,5-triazine, ethanamide, propanamide, butanamide,        pentanamide, hexanamide, heptanamide, octanamide, nonanamide,        decanamide, dodecanamide, tetradecanamide, hexadecanamide, and        octadecanamide.

In an embodiment, the composition of the biodegradable, hydrophobicpolymer(s) further comprises, 0.1-5.0% of the polymer weight a)polyamines comprising of one or more members selected from the groupconsisting of:

-   -   ethylenediamine, diethylenetriamine, triethylenetetramine        tetraethylenepentamine and aminoethylethanolamine,

-   b) one or more polyol compounds selected form the group consisting    of:    -   trimethylol propane, trimethylol ethane, pentaerythritol,        sorbitol and sorbitan, glucose, fructose, galactose, and        glycerin, poly(C₁₋₁₀ alkylene) glycols, ethylene glycol, 1,3        propylene glycol, 1,2 propylene glycol, and butylene glycol, and

-   c) one or more monoprotic compound(s) selected from the group    consisting of:    -   diethylamine, diethanolamine, methylethanolamine,        diisopropanolamine, methylispropylamine, cyclohexalamine,        methanol, ethanol, butanol, hexanol, isopropylidene glycerol,        tripropylene glycol methyl ether, tripropylene glycol butyl        ether, dipropylene glycol butyl ether and tripropylene glycol        butyl ether.

In an embodiment, the composition of the one or more biodegradablehydrophobic polymers is present in an amount that is between about 5-65%of a total composition.

In an embodiment, the composition of the biodegradable, hydrophobicpolymers which comprises the reaction products of aldehyde(s) andnitrogen containing compounds dispersed in NOSDS further comprises oneor more of surfactants, buffers, fragrance/odor masking agents,colorants, flow modifiers, silicas, hydrophobized silicas, one or morebiologically active agents selected from the group consisting of a)urease inhibitors, nitrification inhibitors, pesticides, herbicidesfungicides(s), and insecticide(s) and one or more catalysts selectedfrom the group consisting of methane sulfonic acid, sulfuric acid,para-toluene sulfonic acid, phosphoric acid and methane phosphonic acid.

In an embodiment, the composition of the biodegradable, hydrophobicpolymers comprise the reaction products of aldehyde(s) and nitrogencontaining compounds dispersed in NOSDS wherein said aldehyde comprisesparaformaldehyde. In an embodiment, said nitrogen containing compoundscomprise dicyandiamide and said NOSDS is dimethyl sulfoxide. In avariation, the composition further comprises one or more of surfactants,buffers, fragrance/odor masking agents, colorants, flow modifiers,silicas, hydrophobized silicas, one or more biologically active agentsselected from the group consisting of a) urease inhibitors,nitrification inhibitors, pesticides, herbicides fungicides(s), andinsecticide(s) and one or more catalysts selected from the groupconsisting of methane sulfonic acid, sulfuric acid, para-toluenesulfonic acid, phosphoric acid and methane phosphonic acid.

In an embodiment, the method of use of the composition comprisingdicyandiamide, paraformaldehyde and dimethyl sulfoxide that provideshigh levels of the nitrification inhibitor, dicyandiamide, is as acoating onto fertilizer granules. Alternatively and/or additionally, thecomposition can be added to anhydrous ammonia for direct injection intothe soil to provide extended availability of nutrients for plant growththrough inhibiting the conversion of ammonia to nitrate.

In an embodiment, the method for making the composition of thebiodegradable, hydrophobic polymers which comprises the reactionproducts of aldehyde(s) and nitrogen containing compounds dispersed inNOSDS for application to fertilizer comprises adding biodegradablehydrophobic polymers that are the reaction product of aldehydes andnitrogen containing compound powders to the NOSDS under agitation attemperatures of 15-140° C., and optionally using a high shear mixer toreduce viscosity of the mixture.

In an embodiment, the present invention relates to a method for makingthe composition of the biodegradable, hydrophobic polymers whichcomprises the reaction products of aldehyde(s) and nitrogen containingcompounds dispersed in NOSDS for application to fertilizer. In avariation, the method comprises adding a) biodegradable hydrophobicpolymers that involves the reaction of aldehydes and nitrogen containingcompound that are pre-dispersed in a liquid with undesirable propertiessuch as flash point, health, shipping or environmental hazards and/ordestabilize components of fertilizer or additives to the fertilizer tob) a NOSDS in which the liquid is displaced through differential boilingpoints by temperature and/or reduced pressure.

In an embodiment, the present invention relates to a method for makingthe composition of the biodegradable, hydrophobic polymers whichcomprises the reaction products of aldehyde(s) and nitrogen containingcompounds dispersed in NOSDS for application to fertilizer comprised ofprocuring 1) one or more aldehydes represented by the structure:

-   -   where Q is: O, S    -   where R¹¹ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —CH═CH₂,        —C₄H₃O, —C₇H₇, —C₆H₅, —C₆H₁₁, CHO, C₂H₃O, C₃H₅O, C₄H₇O, C₇H₅O or        —R¹²O₂R¹³,    -   where R¹² is: —C, —C₂H₂, —C₃H₄, —C₄H₆, —C₅H₈, —C₆H₁₀    -   where R¹³ is: —H, CH₃, C₂H₃, C₃H₇, C₄H₉

and reacting said aldehydes with 2) one or more nitrogen containingcompounds selected from the group represented by the structures:

-   -   where A is: O, S    -   where R¹⁴ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(a)NH₂    -   where a is an integer: 1-10    -   where R¹⁵ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(b)NH₂    -   where b is an integer: 1-10    -   where R¹⁶ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(c)NH₂    -   where c is an integer: 1-10    -   where R¹⁷ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(d)NH₂    -   where d is an integer: 1-10,

and their tautomeric forms,

-   -   where X₁ is: —NHR¹⁸, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   where R¹⁸ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂, C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅    -   where X₂ is: —NHR¹⁹, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   where R¹⁹ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂, —C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅    -   where X₃ is: —NHR²⁰, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   where R²⁰ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂, —C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅        and d)    -   NH₂CO—R²¹    -   where R²¹ is an alkyl radical CH₃ to —C₁₇H₃₅        3) dispersing the nitrogen containing compound(s) at        temperatures of 10-140° C. into a non-aqueous organo solvent        delivery system (NOSDS), wherein the NOSDS comprises one or more        aprotic solvents selected from the group consisting of 1)        dimethyl sulfoxide and 2) dialkyl, diaryl, or alkylaryl        sulfoxide(s) having the formula:

R₉S(O)_(x)R₁₀

-   -   wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylene group,        an aryl group, or C₁₋₃alkylenearyl group or R₉ and R₁₀ together        with the sulfur to which they are attached form a 4 to 8        membered ring wherein R₉ and R₁₀ together are a C₁₋₆ alkylene        group which optionally contains one or more atoms selected from        the group consisting of O, S, Se, Te, N, and P in the ring and x        is 1 or 2, and optionally further comprising    -   one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate, 4) one or more polyols capped with acetate        or formate wherein the polyol portion selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and glycerin, 5) one or more        alkylene glycol alkyl ethers acetates selected from the group        consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and tripropylene        glycol butyl ether acetate and, 6) isophorone, 7) one or more        diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate, 8) dimethylacetamide, 9)        dimethylformamide, 10) dimethyl-2-imidazolidinone, 11)        1-Methyl-2-pyrrolidone, 12) hexamethylphosphoramide, 13)        1,2-dimethyloxyethane, 14) 2-methoxyethyl ether, 15)        cyclohexylpyrrolidone and 16) limonene,

-   4) wherein said composition is cooled to 30-60° C. and the aldehydes    are charged at a rate that controls the exotherm with 5-20° C. of    the reaction temperature of 30-70° C. in a molar ratio of aldehyde    to aldehyde reactive sites on the nitrogen containing compound of    0.10-0.90/1.0;

-   5) wherein the reaction is held at 30-70° C. and at a pH of 7.5-10.0    for 1 to 12 hours until the free formaldehyde is 40,000-5,000 ppm's;    and

-   6) wherein the pH is adjusted to 4.0-6.5, and the reaction is heated    to 70-115° C.,

-   7) wherein the reactor is optionally placed under a vacuum with a    nitrogen sparge of 0.1 mm to 200 mm and held until free formaldehyde    is <700 ppm, and then the composition is cooled.

In an embodiment, the present invention relates to a process forapplying the composition of the biodegradable, hydrophobic polymers saidprocess comprising adding the reaction products of aldehyde(s) andnitrogen containing compounds dispersed in NOSDS to fertilizer granules.In an embodiment, the process comprises:

-   -   1) placing the fertilizer granules in blending equipment        comprising one or more pieces of equipment selected from the        group consisting of mixers, blenders and tumblers or on a        conveyer belt    -   2) applying the composition to said fertilizer granules at a        temperature of 15-130° C. through a metering or a spray        injection system; and    -   3) mixing or spraying until the fertilizer granules show        complete coverage.

In an embodiment, the present invention relates to a compositioncomprising one or more biodegradable hydrophobic polymers of a molecularweight range of 50-200,000 Daltons, a crosslinking agent and aNon-aqueous Organo Solvent Delivery System (NOSDS), wherein saidcomposition is a stable dispersion ideally suited to coat man-madeand/or natural fertilizer components, wherein the biodegradable,hydrophobic polymers comprise the reaction products of aldehyde(s) andnitrogen containing compounds and wherein the NOSDS is comprised of oneor more aprotic solvents selected from the group consisting of 1)Dimethyl Sulfoxide and 2) dialkyl, diaryl, or alkylaryl sulfoxide(s)having the formula:

R₉S(O)_(x)R₁₀

-   -   wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylene group,        an aryl group, or    -   C₁₋₃alkylenearyl group or R₉ and R₁₀ with the sulfur to which        they are attached form a 4 to 8 membered ring wherein R₉ and R₁₀        together are a C₁₋₆ alkylene group which optionally contains one        or more atoms selected from the group consisting of O, S, Se,        Te, N, and P in the ring and x is 1 or 2,    -   and optionally further comprising        3) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate, 4) one or more polyols capped with acetate        or formate wherein the polyol portion selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and glycerin, 5) one or more        alkylene glycol alkyl ethers acetates selected from the group        consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and tripropylene        glycol butyl ether acetate and, 6) isophorone, 7) one or more        diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate, 8) dimethylacetamide, 9)        dimethylformamide, 10) dimethyl-2-imidazolidinone, 11)        1-Methyl-2-pyrrolidone, 12) hexamethylphosphoramide, 13)        1,2-dimethyloxyethane, 14) 2-methoxyethyl ether,        15)cyclohexylpyrrolidone and 16) limonene.

In a variation, the aldehyde(s) is comprised of one or more compoundsrepresented by the structure:

-   -   where Q is: O, S    -   where R¹¹ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —CH═CH₂,        —C₄H₃O, —C₇H₇, —C₆H₅, —C₆H₁₁, CHO, C₂H₃O, C₃H₅O, C₄H₇O, C₇H₅O or        —R¹²O₂R¹³,    -   where R¹² is: —C, —C₂H₂, —C₃H₄, —C₄H₆, —C₅H₈, —C₆H₁₀    -   where R¹³ is: —H, CH₃, C₂H₃, C₃H₇, C₄H₉

wherein the nitrogen containing compound comprises one or more compoundsrepresented by the structures:

-   -   where A is: O, S    -   where R¹⁴ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(a)NH₂    -   where a is an integer: 1-10    -   where R¹⁵ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(b)NH₂    -   where b is an integer: 1-10    -   where R¹⁶ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(c)NH₂    -   where c is an integer: 1-10    -   where R¹⁷ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃, —C₆H₅, —CONH₂,        —(CONH)_(d)NH₂    -   where d is an integer: 1-10,

and their tautomeric forms,

-   -   where X₁ is: —NHR¹⁸, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   where R¹⁸ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂, C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅    -   where X₂ is: —NHR¹⁹, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   where R¹⁹ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂, —C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅    -   where X₃ is: —NHR²⁰, —H, —OH, —C₆H₅, —N(CH₃)₂, —CH₃    -   where R²⁰ is: H, an alkyl radical —CH₃ to —C₁₂H₂₅, —C₂H₄OC₂H₄OH,        C₂H₄OC₂H₄NH₂, —C₃H₆—N(CH₃)₂, C₂H₄OH, —C₆H₅        and

-   NH₂CO—R²¹    -   where R²¹ is an alkyl radical CH₃ to —C₁₇H₃₅        wherein a crosslinking agent is comprised of one or more of        compounds represented by the structures:

In an embodiment, the present invention relates to a composition of thebiodegradable, hydrophobic polymers which comprises the reactionproducts of aldehyde(s) and nitrogen containing compounds dispersed inNOSDS wherein the one or more biodegradable hydrophobic polymers arepresent in an amount that is between about 5-65% of a total composition.In a variation, the crosslinking agent is present in an amount that isbetween about 0.1-10% of the total composition.

In an embodiment, the composition of the biodegradable, hydrophobicpolymers which comprises the reaction products of aldehyde(s) andnitrogen containing compounds dispersed in NOSDS, further comprising oneor more of surfactants, buffers, fragrance/odor masking agents,colorants, flow modifiers, silicas, hydrophobized silicas, one or morebiologically active agents selected from the group consisting of a)urease inhibitors, nitrification inhibitors, pesticides, herbicidesfungicides(s), and insecticide(s) and one or more catalysts selectedfrom the group consisting of methane sulfonic acid, sulfuric acid,para-toluene sulfonic acid, phosphoric acid and methane phosphonic acid.

In an embodiment, the present invention relates to compositions andmethods of making a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors comprised ofutilizing a non-aqueous polar, aprotic organo liquid (NAPAOL) as thereaction medium for the reaction of aldehyde(s) with cyano-containingnitrification inhibitors that have one or more aldehyde reactive groupsselected from the group consisting of a) primary amines, b) secondaryamines, c) amides, d) thiols, e) hydroxyls and f) phenols, wherein oneor more of the following variants are met:

-   -   1. the reaction medium does not contain water as many nitrogen        source application techniques are sensitive to the presence of        moisture. The presence of water can alsolead to the degradation        of the cyano-group to diaminomethylene urea under reaction        conditions,    -   2. the reaction medium must be aprotic to prevent any solvent        reaction with aldehydes,    -   3. the reacting materials and fmal product must be or become        soluble in the reaction medium,    -   4. the reaction does not require aldehyde reactive,        non-nitrification compounds (outside of catalyst) such as urea        or ammonia in order to facilitate the reaction of aldehyde with        a nitrification inhibitor,    -   5. the reaction medium can also serve as the solvent delivery        system for applications to nitrogen sources utilizing one or        more application techniques selected from the group consisting        of a) coating the surface of fertilizer granules/prills, b)        dispersing the liquid invention into an aqueous nitrogen source        such as UAN, c) dispersing the liquid invention into ammonical        sub-surface injections, d) aiding in dissolving the liquid        invention directly into molten nitrogen sources such as urea,    -   6. the reaction medium also serves as the solvent for        incorporating biologically active agents and naturally occurring        substances, substances produced by natural processes such as        fermentation and/or extracts of naturally occurring substances        (termed as biologics) such as but not limited one or more        members selected from the group consisting of urease inhibitors,        nitrification inhibitor(s), pesticide(s), herbicide(s),        fungicides(s), and insecticide(s),    -   7. the reaction conditions are selected which favor the        conservation of the cyano-group,    -   8. the fmal product is dispersed in a non-aqueous liquid,    -   9. the level of free aldehyde in the final product is less than        700 ppm.

In an embodiment, a method of making a liquid fertilizer additive ofbiodegradable polymeric and/or oligomeric nitrification inhibitors iscomprised of utilizing NAPAOL as the reaction medium for the reaction ofaldehyde(s) with cyano-containing nitrification inhibitors that have oneor more aldehyde reactive groups selected from the group consisting ofa) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols wherein the resulting product possesses one ormore of the following improvements over reactions performed in anaqueous medium:

-   -   1. better control over polymer distribution resulting from the        proper selection of process conditions,    -   2. lower water solubility results in slower dissolution of        nitrogen sources and added biological actives once applied to        the soil,    -   3. slow the loss of nitrification inhibition by reducing the        nitrification inhibitors' volatility, limiting migration through        the soil by increasing its molecular weight which lowers the        nitrification inhibitors' water solubility,    -   4. extending the nitrification inhibitors' lifespan by utilizing        incorporation into a polymer backbone which through        biodegradation results in a slow release of incorporated        nitrification inhibitors,    -   5. retaining some nitrification inhibition capability through        formation of methylene bis nitrification inhibitor oligomers        based on the reaction product of a total 2 moles of one or more        nitrifications inhibitors that contain 1 to 2 aldehyde reactive        groups reacted with one mole of aldehyde,    -   6. lower viscosity versus polymers formed in an aqueous medium        which aides in coating solid nitrogen sources and adding to        aqueous nitrogen sources as well as non-agricultural processes        either further chemically modified or unmodified such as but not        limited to industrial processes such as waste water color        removal, paint detackification and treatment of paint or oily        waste water and the treatment of leather,    -   7. able to maintain said biodegradable polymers at levels of        1-80% as liquids in a NAPAOL to temperatures down to at least        10° C. meaning that these compositions have improved shelf        storage lives,    -   8. able to provide improved and even delivery of the liquid        invention to the surface of fertilizer granules and solid        nitrogen sources of said biodegradable polymeric/oligomeric        nitrification inhibitors while not causing clumping of the        granules,    -   9. able to safely incorporate into non-aqueous liquid nitrogen        sources such as pressurized anhydrous ammonia gas,    -   10. able to incorporate directly into molten nitrogen sources a        non-aqueous liquid product that results in better distribution        of the said biodegradable polymeric/ oligomeric nitrification        inhibitors throughout the molten mass,    -   11. able to achieve higher concentration levels of the total of        polymer bound and free nitrification inhibitors versus        non-aqueous polar aprotic organo solvated free only        nitrification inhibitors,    -   12. process yields a liquid product with an aldehyde content of        <700 ppm.

In an embodiment, a method of making liquid fertilizer additives ofbiodegradable polymeric and/or oligomeric nitrification inhibitors iscomprised of utilizing a NAPAOL as the reaction medium for the reactionof aldehyde(s) with cyano-containing nitrification inhibitors that haveone or more aldehyde reactive groups selected from the group consistingof a) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols results in a product for direct application tonitrogen sources.

In an embodiment, a method of making liquid fertilizer additives ofbiodegradable polymeric and/or oligomeric nitrification inhibitorscomprised of utilizing a NAPAOL as the reaction medium for the reactionof aldehyde(s) with cyano-containing nitrification inhibitors that haveone or more aldehyde reactive groups selected from the group consistingof a) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols is designed wherein the molar ratio is set toensure that the aldehyde to aldehyde reactive groups ratio available insaid cyano-containing nitrification inhibitors is such that the aldehydeis completely reacted to its methylene form versus the methylolfunction.

—NI—CH₂—NI vs —NI—CH₂—OH

In a variation, the molar ratio of said aldehyde to saidcyano-containing nitrification inhibitors is set with an excess ofaldehyde reactive groups to ensure low free aldehyde products.

In an embodiment, a method of making fertilizer additives ofbiodegradable polymeric and/or oligomeric nitrification inhibitors iscomprised of utilizing a NAPAOL as the reaction medium for the reactionof aldehyde(s) with cyano-containing nitrification inhibitors that haveone or more aldehyde reactive groups selected from the group consistingof a) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols wherein to conserve the cyano-function of thenitrification inhibitors, one or more of the following reactionparameters are utilized: 1) limit the presence of water throughout thereaction, 2) minimize the temperature of any acid catalyst addition, and3) minimize reaction time and/or temperature. In an embodiment, thereare two reactions that occur. A first reaction is the aldehyde reactionwith the amine and other groups as shown above and the second is thereaction of the methylol group with an aldehyde reactive group (as shownabove), which is a reaction that can be accomplished in one embodimentby the addition of an acid catalyst. The reaction temperature shouldremain below about 70° C. for the addition of acid catalyst. It shouldbe understood that as one increases the temperature, the time can bedecreased and vice versa. In an embodiment, the time may range fromabout 8 hours to 32 hours. In an embodiment, it should be understoodthat water may be removed as the second reaction proceeds to furtherincrease yield of the reaction product.

In an embodiment, a method of making fertilizer additives ofbiodegradable polymeric and/or oligomeric nitrification inhibitors iscomprised of utilizing a NAPAOL as the reaction medium for the reactionof aldehyde(s) with cyano-containing nitrification inhibitors that haveone or more aldehyde reactive groups selected from the group consistingof a) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols comprises the following steps:

-   -   A) procurement of        -   1) one or more aldehydes represented by the structure:

-   -   -   -   wherein Q is: O, S            -   wherein R¹¹ is: —H, alkyl radical —C₁H₃ to —C₆H₁₃,                —CH═CH₂, —C₄H₃O, —C₇H₇, —C₆H₅, —C₆H₁₁, CHO, C₂H₃O,                C₃H₅O, C₄H₇O, C₇H₅O or —R¹²O₂R¹³,            -   wherein R¹² is: —C, —C₂H₂, —C₃H₄, —C₄H₆, —C₅H₈, —C₆H₁₀            -   wherein R¹³ is: —H, CH₃, C₂H₃, C₃H₇, and C₄H₉

        -   2) one or more cyano-containing nitrification inhibitors            that have one or more aldehyde reactive groups selected from            the group consisting of a) primary amines, b) secondary            amines, c) amides, d) thiols, e) hydroxyls and f) phenols            selected from the group consisting of:            -   a) one or more cyano-compounds selected from the group                represented by the structures

-   -   -   3) a non-aqueous polar aprotic organo liquid, wherein the            non-aqueous polar, aprotic solvent (NAPAOL) is the reaction            medium, which comprises one or more members selected from            the group consisting of            -   a) dimethyl sulfoxide            -   b) and dialkyl, diaryl, or alkylaryl sulfoxide(s) having                the formula:

R₉S(O)_(x)R₁₀

-   -   -   -   wherein R₉ and R₁₀ are each independently a C₁₋₆                alkylene group, an aryl group, or C₁₋₃alkylenearyl group                or R₉ and R₁₀ together with the sulfur to which they are                attached form a 4 to 8 membered ring wherein R₉ and R₁₀                together are a C₁₋₆ alkylene group which optionally                contains one or more atoms selected from the group                consisting of O, S, Se, Te, N, and P in the ring and x                is 1 or 2.            -   c) and one or more alkylene carbonates selected from the                group consisting of ethylene carbonate, propylene                carbonate and butylene carbonate d)                1-Methyl-2-pyrrolidone, e) one or more organo                phosphorous liquids selected from the group consisting                of hexamethylphosphoramide and one or more                trialkylphosphates selected from the group represented                by the formula.

-   -   -   -   -   wherein:                -    R₂₂ is alkyl radical —C₁H₃ to —C₆H₁₃                -    R₂₃ is alkyl radical —C₁H₃ to —C₆H₁₃                -    R₂₄ is alkyl radical —C₁H₃ to —C₆H₁₃

            -   f) 1,2-dimethyloxyethane, g) 2-methoxyethyl ether and h)                cyclohexylpyrrolidone

    -   B) a reaction vessel may be equipped with agitation, heating and        cooling (hot oil systems are not recommended), riser, overhead        condenser and a receiving vessel to capture reaction distillate,        capable of a vacuum of 0.5-50 mm and sparging/sweeping with an        inert gas such as but not limited to nitrogen and carbon dioxide

    -   C) charging said procured ingredients to said reactor by one or        more steps selected from the group consisting of:        -   a) charging said aldehydes, said cyano-nitrification            inhibitors and said NAPAOL to said reaction vessel and start            mixing        -   b) charging said cyano-containing nitrification inhibitors            and said NAPAOL to said reaction vessel, start mixing and            heating mixture to 40-90° C., holding for 0-60 minutes at            temperature, cooling down to 20-60° C. and then charging            said aldehyde.        -   c) charging said cyano-containing nitrification inhibitors            and said NAPAOL to said reaction vessel, de-oxygenate the            vessel by either sparging with an inert gas such as but not            limited to nitrogen and carbon dioxide for a 15-60 minutes            or by placing vessel under vacuum and breaking vacuum by            sparging/sweeping vessel with an inert gas and repeating            this exercised-oxygenation at least 3 times and then            charging said aldehyde.

    -   D) proceeding with the first reaction by one or more steps        selected from the group consisting of:        -   a) heating contents of the vessel to 50-90° C. and hold at            temperature for 1-4 hours,        -   b) heating contents of the vessel to 70-80° C. and hold at            temperature for 1-4 hours        -   c) heating contents of the vessel to 50-90 C and hold at            temperature until contents are clear        -   d) heating contents of the vessel to 70-80° C. and hold at            temperature until contents are clear.

    -   E) proceeding with the second reaction by one or more steps        selected from the group consisting of:        -   a) placing reaction vessel under a vacuum of 0.5-50 mm,            increasing temperature to 90-120° C. and held under vacuum            and at temperature until aldehyde content is 0-700 ppm.        -   b) charging an acid catalyst such as but not limited to one            or more members selected from the group consisting of            methane sulfonic acid, sulfuric acid, para-toluene sulfonic            acid phosphoric acid and methane phosphonic acid, placing            reaction vessel under a vacuum of 0.5-50 mm, increasing            temperature to 90-120° C. and hold under vacuum and at            temperature until aldehyde content is 0-700 ppm. In a            variation, cooling contents of reaction vessel, if            necessary, to 20-60° C. before charging the acid catalyst

    -   F) terminating the reaction by one or more steps selected from        the group consisting of:        -   a) hard sparging reaction vessel contents with an inert gas            to assist in removing residual aldehyde. Vacuum and hard            sparge can be repeated to assist in removing aldehyde from            the contents in the reaction vessel.        -   b) Ensuring ppm formaldehyde is <700 ppm.        -   c) cooling contents below 40° C. and off load        -   d) charging a mild neutralizing agent such as            triethanolamine to neutralize the acid catalyst.

In a variation, the acid catalyst is added in an amount that ensuresthat the pH of 5% by weight of the fmal product in aqueous solution willbe greater than 7.0.

In an embodiment, a method of making liquid fertilizer additives ofbiodegradable polymeric and/or oligomeric nitrification inhibitors iscomprised of utilizing a NAPAOL as the reaction medium for the reactionof aldehyde(s) with cyano-containing nitrification inhibitors that haveone or more aldehyde reactive groups selected from the group consistingof a) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols comprises reacting cyano-containingnitrification inhibitors with aldehydes at a molar ratio ofcyano-containing nitrification inhibitors' aldehyde reactive units toaldehyde units of 1:1. In an embodiment, using NAPAOL as the reactionmedium results in a composition of wherein at least 70% or alternativelyat least 90% of the total nitrification inhibitor content is apolymeric/oligomeric compound. In a variation, the reaction product canbe dispersed within 20-80% NAPAOL.

In an embodiment, reaction product of cyano-containing nitrificationinhibitors with aldehydes comprise a molar ratio of cyano-containingnitrification inhibitors' aldehyde reactive units to aldehyde units of1:1 to 2:1. In an embodiment using NAPAOL as the reaction medium resultsin a composition wherein at least 50% or alternatively at least 70% ofthe total nitrification inhibitor content is a polymeric compound. In avariation, the reaction product can be dispersed within 20-80% NAPAOL.

In an embodiment, reaction product of cyano-containing nitrificationinhibitors with aldehydes comprise a molar ratio of cyano-containingnitrification inhibitors' aldehyde reactive units to aldehyde units of2:1 to 4:1. In an embodiment using NAPAOL as the reaction medium resultsin a composition of wherein at least 30% or alternatively at least 51%of the total nitrification inhibitors content as polymeric/oligomericcompounds. In a variation, the reaction product can be dispersed within20-80% NAPAOL.

In an embodiment, a method of making liquid fertilizer additives ofbiodegradable polymeric and/or oligomeric nitrification inhibitorscomprises utilizing the NAPAOL dimethyl sulfoxide (DMSO) as the reactionmedium for the reaction of paraformaldehyde with dicyandiamide (DCD) Ina variation, a method of making a liquid fertilizer additive ofbiodegradable polymeric and/or oligomeric nitrification inhibitorscomprises reacting a molar ratio of DCD to formaldehyde of 1:1 within(DMSO) resulting in a composition wherein at least 70% or alternativelyat least 90% of the total nitrification inhibitor content is a polymericcompound. In a variation, the reaction product can be dispersed within20-80% DMSO. In another variation, a method of making a liquidfertilizer additive of biodegradable polymeric and/or oligomericnitrification inhibitors comprises reacting a molar ratio of DCD toformaldehyde of 1:1 to 2:1 within DMSO resulting in a composition ofwherein at least 50% or alternatively at least 70% of the totalnitrification inhibitor content is a polymeric compound. In a variation,the reaction product can be dispersed within 20-80% DMSO.

In another variation, a method of making a liquid fertilizer additive ofbiodegradable polymeric and/or oligomeric nitrification inhibitorscomprises reacting a molar ratio of DCD to formaldehyde of 2:1 to 4:1within DMSO resulting in a composition of wherein at least 30% oralternatively at least 50% of the total nitrification inhibitor contentis a polymeric compound. In a variation, the reaction product can bedispersed within 20-80% DMSO.

In a variation, the reaction product of DCD reacted withparaformaldehyde comprises a molar ratio of DCD to formaldehyde unit of4:1 wherein the DMSO is the reaction medium results in a composition ofapproximately 51.9% of the total nitrification inhibitor content as anoligomeric compound and approximately 48.1% free DCD.

In an embodiment, a method of making fertilizer additives or a liquidcomposition of biodegradable polymeric and/or oligomeric nitrificationinhibitors is comprised of utilizing a NAPAOL as the reaction medium forthe reaction of aldehyde(s) with cyano-containing nitrificationinhibitors that have one or more aldehyde reactive groups selected fromthe group consisting of a) primary amines, b) secondary amines, c)amides, d) thiols, e) hydroxyls and f) phenols comprise DCD reacted withparaformaldehyde at a molar ratio of DCD to formaldehyde unit of up to4:1 wherein the NAPAOL, dimethyl sulfoxide (DMSO), is the reactionmedium resulting in a composition of approximately 51.9% of the totalnitrification inhibitor content as an oligomeric compound andapproximately 48.1% free DCD wherein the total concentration of polymerbound and free DCD is 10-60% and the DMSO is 40 to 90% of said liquidfertilizer additives.

In a variation, the DCD reacted with paraformaldehyde at a molar ratioof DCD to formaldehyde unit of up to a 4:1 wherein DMSO, is the reactionmedium possesses better water solubility versus a DCD/paraformaldehydereaction product based on a 2:1 molar wherein the compositional ratio isadjusted to 51.9/48.1 of polymer to free DCD at elevated temperatures of40-90° C. and equivalent compositional amounts of DMSO.

In an embodiment, a method of making fertilizer additives ofbiodegradable polymeric and /or oligomeric nitrification inhibitors iscomprised of utilizing a NAPAOL as the reaction medium for the reactionof aldehyde(s) with cyano-containing nitrification inhibitors that haveone or more aldehyde reactive groups selected from the group consistingof a) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols comprise DCD reacted with paraformaldehyde at amolar ratio of DCD to formaldehyde unit of 1:1 to 2:1 wherein theNAPAOL, dimethyl sulfoxide (DMSO), is the reaction medium resulting in acomposition of at least 70% of the total nitrification inhibitor contentas a polymeric compound wherein the total concentration of polymer boundand free DCD is 10-80%. In a variation, free DCD can be added to theformulation wherein the composition of free DCD is adjusted to 1-60% ofthe total of free and polymer bound. When free DCD is present, itincreases the initial performance of the product as a nitrificationinhibitor.

In an embodiment, a method of making liquid fertilizer additives ofbiodegradable polymeric and/or oligomeric nitrification inhibitors iscomprised of utilizing a NAPAOL as the reaction medium for the reactionof aldehyde(s) with cyano-containing nitrification inhibitors that haveone or more aldehyde reactive groups selected from the group consistingof a) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols may further comprise the addition, during thealdehyde reaction, of polyamines comprising one or more members selectedfrom the group consisting of ethylenediamine, diethylenetriamine,triethylenetetramine tetraethylenepentamine and aminoethylethanolaminewhereas the polyamines comprise 0.01-5% of the polymer compositionweight in order to modify the coatings' properties such ashydrophobicity, coverage, flexibility of the formed film. In avariation, ammonia is added during the formaldehyde reaction. By polymercomposition weight, it is meant the nitrification inhibitor compositionweight.

In an embodiment, a method of making liquid fertilizer additives ofbiodegradable polymeric and/or oligomeric nitrification inhibitors iscomprised of utilizing a NAPAOL as the reaction medium for the reactionof aldehyde(s) with cyano-containing nitrification inhibitors that haveone or more aldehyde reactive groups selected from the group consistingof a) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols may further comprise the addition, during thealdehyde reaction, of polyols comprising one or more members selectedfrom the group consisting of and/or compounds such as but not limited toone or more polyols selected from the group consisting of 1) trimethylolpropane, trimethylol ethane, pentaerythritol, sorbitol and sorbitan,glucose, fructose, galactose, and glycerin, 2) poly(C₁₋₁₀ alkylene)glycols, 3) one or more alkylene glycols from the group consisting ofethylene, 1,3 propylene glycol, 1,2 propylene glycol, and butyleneglycol, 4) isopropylidene glycerol 5) one or more alkylene glycol alkylethers from the group consisting of tripropylene glycol methyl ether,tripropylene glycol butyl ether, dipropylene glycol butyl ether andtripropylene glycol butyl ether whereas the polyols comprise 0.1-5% ofthe polymer weight in order to modify the coatings' properties such ashydrophobicity, coverage, flexibility of the formed film.

In an embodiment, the present invention relates to a method of making aliquid fertilizer additive of biodegradable polymeric and/or oligomericnitrification inhibitors is comprised of utilizing a NAPAOL as thereaction medium for the reaction of aldehyde(s) with cyano-containingnitrification inhibitors that have one or more aldehyde reactive groupsselected from the group consisting of a) primary amines, b) secondaryamines, c) amides, d) thiols, e) hydroxyls and f) phenols, wherein thesecondary amines may comprise one or more members selected form thegroup consisting of diethanolamine, diethylamine, cyclohexylamine,methylethanolamine, diisopropanolamine, methylispropylamine. In anembodiment, the secondary amines may comprise 0.1-5% of the polymerweight to assist in controlling the molecular weight build of thebiodegradable polymeric and/or oligomeric nitrification inhibitorsthrough chain termination.

In an embodiment, the present invention relates to a method of makingliquid fertilizer additives of biodegradable polymeric and/or oligomericnitrification inhibitors is comprised of utilizing a NAPAOL as thereaction medium for the reaction of aldehyde(s) with cyano-containingnitrification inhibitors that have one or more aldehyde reactive groupsselected from the group consisting of a) primary amines, b) secondaryamines, c) amides, d) thiols, e) hydroxyls and f) phenols, wherein theadditives may further comprise addition of low molecular weight alcohols(during the formaldehyde reaction) wherein the low molecular weightalcohols comprise one or more members selected from the group consistingof methanol, ethanol, butanol, and hexanol. In an embodiment, the lowmolecular weight alcohols comprise 0.1-5% of the polymer weight toassist in controlling the molecular weight build of the biodegradablepolymeric and/or oligomeric nitrification inhibitors through chaintermination.

In an embodiment, the composition of liquid fertilizer additivecomprising utilizing a NAPAOL as the reaction medium for the reaction ofaldehyde(s) with cyano-containing nitrification inhibitors that have oneor more aldehyde reactive groups selected from the group consisting ofa) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols, wherein the composition may further comprisethe addition of one or more alkoxy capped monomers selected from thegroup consisting of 1,3,4,6-tetrakis(methoxymethyl)glycoluril,N,N,N′,N′,N″,N″-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine,tetra(methoxymethyl) urea and di(methoxymethyl) urea for coating offertilizer granules to promote further crosslinking of compoundscontaining aldehyde reactive groups on the surface of the fertilizergranule and with the surface of urea granules and for adding to moltenurea to increase crosslinking of compounds containing aldehyde reactivegroups and reaction with the urea. In a variation, the composition canfurther comprise urea-formaldehyde polymers, ammonia-formaldehydepolymers, urea-ammonia-formaldehyde polymer and triazone-formaldehydestructures.

In a variation, the present invention relates to a composition or liquidfertilizer additives of biodegradable polymeric and/or oligomericnitrification inhibitors is comprised of utilizing a NAPAOL as thereaction medium for the reaction of aldehyde(s) with cyano-containingnitrification inhibitors that have one or more aldehyde reactive groupsselected from the group consisting of a) primary amines, b) secondaryamines, c) amides, d) thiols, e) hydroxyls and f) phenols, wherein thecomposition may further comprise one or more of members selected fromthe group consisting of surfactants, buffers, fragrance/odor maskingagents, colorants, flow modifiers, silicas, hydrophobized silicas and/orone or more catalysts selected from the group consisting of methanesulfonic acid, sulfuric acid, para-toluene sulfonic acid, phosphoricacid and methane phosphonic acid.

In another variation, the composition may optionally contain one or morebiologically active agents and/or biologics selected from the groupconsisting of a) urease inhibitors, nitrification inhibitors,pesticides, herbicides fungicides(s), and insecticide(s).

In an embodiment, the post reaction composition of liquid fertilizeradditive comprising biodegradable polymeric and/or oligomericnitrification inhibitors using a NAPAOL as the reaction medium for thereaction of aldehyde(s) with cyano-containing nitrification inhibitorsthat have one or more aldehyde reactive groups wherein the reactivegroups are selected from the group consisting of a) primary amines, b)secondary amines, c) amides, d) thiols, e) hydroxyls and f) phenols mayfurther comprise one or more non-aqueous organo liquids selected fromthe group consisting of polar aprotic, aprotic and protic organosolvents wherein these groups are as follows:

-   -   a) one or more aprotic solvents selected from the group        consisting of 1) one or more polyols capped with acetate or        formate wherein the polyol portion selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and glycerin, 2) one or more        alkylene glycol alkyl ethers acetates selected from the group        consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and tripropylene        glycol butyl ether acetate and, 3) isophorone, 4) one or more        diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate, 5) dimethylacetamide, 6)        dimethylformamide, 7) dimethyl-2-imidazolidinone, 8)        1-Methyl-2-pyrrolidone and 9) limonene,    -   b) one or more protic solvents selected from the group        consisting of: 1) an alcohol from the family of C₁₋₁₀        alkanols, 2) one or more polyols selected from the group        consisting of trimethylol propane, trimethylol ethane,        pentaerythritol, sorbitol, sorbitan, glucose, fructose,        galactose, and glycerin, 3) one or more poly(C₁₋₁₀ alkylene)        glycols represented by the structure:

H(C_(t)H_(u))_(v)OH

-   -   -   t is an integer: 1-10        -   u is an integer: 2-20        -   and v is an integer: 1-20,

    -   4) one or more alkylene glycols selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, and butylene glycol, 5) isopropylidene        glycerol 6) one or more alkylene glycol alkyl ethers selected        from the group represented by the structure:

-   -   -   wherein R¹ is: CH₃, C₂H₅, C₃H₇ or C₄H₉        -   wherein R² is: H or the structure

-   -   -   wherein R³ is: H or CH₃        -   wherein R⁴ is H and CH₃            -   and f is an integer between 1 and 15,

    -   7) one or more alkyl lactates selected from the group consisting        of ethyl, propyl and butyl lactate, 8) one or more alkanolamines        selected from the group represented by the structure:

-   -   -   wherein R⁵ is: C₂H₄OR⁸ or C₃H₆OH        -   wherein R⁶ is: H, C₂H₄OR⁸ or C₃H₆OH        -   wherein R⁷ is: H, C₂H₄OR⁸ or C₃H₆OH        -   wherein R⁸ is: (C₂H₄O)_(g)H        -   and g is an integer between 1-10,

    -   and 9) glycerol carbonate,

    -   c) and one or more polar aprotic solvents selected from the        group consisting of        -   1) dimethyl sulfoxide        -   2) and dialkyl, diaryl, or alkylaryl sulfoxide(s) having the            formula:

R₉S(O)_(x)R₁₀

-   -   -   -   wherein R₉ and R₁₀ are each independently a C₁₋₆                alkylene group, an aryl group, or C₁₋₃alkylenearyl group                or R₉ and R₁₀ together with the sulfur to which they are                attached form a 4 to 8 membered ring wherein R₉ and R₁₀                together are a C₁₋₆ alkylene group which optionally                contains one or more atoms selected from the group                consisting of O, S, Se, Te, N, and P in the ring and x                is 1 or 2, and optionally further comprising:

        -   3) one or more alkylene carbonates selected from the group            consisting of ethylene carbonate, propylene carbonate and            butylene carbonate 4) 1-Methyl-2-pyrrolidone, 5) one or more            organo phosphorous liquids selected from the group            consisting of hexamethylphosphoramide and one or more            trialkylphosphates selected from the group represented by            the formula.

-   -   -   -   wherein:                -   R₂₂ is alkyl radical —C₁H₃ to —C₆H₁₃                -   R₂₃ is alkyl radical —C₁H₃ to —C₆H₁₃                -   R₂₄ is alkyl radical —C₁H₃ to —C₆H₁₃

        -   6) 1,2-dimethyloxyethane, 7) 2-methoxyethyl ether and 8)            cyclohexylpyrrolidone.

In an embodiment, said non-aqueous organo liquid solvents can be addedto improve the properties of said liquid fertilizer additives, whereinthe properties that can be improved include but are not limited toevenness of the coating, viscosity, solubility in aqueous fertilizersuch as UAN, dispersibility in anhydrous ammonia and dispersibility inurea and modified ureas such as urea formaldehyde polymer (UFP), shelflife stability and cold weather flowability

In another variation, said non-aqueous organo liquid solvents can beadded to impact the properties of the treated nitrogen source such asbut not limited to water resistance, clumping of solid nitrogen sourcesand homogeneity of the dispersion within liquid/molten nitrogen sources.

In a variation, said liquid fertilizer additives may further compriseone or more of members selected from the group consisting ofsurfactants, buffers, fragrance/odor masking agents, colorants, flowmodifiers, silicas, hydrophobized silicas.

In a variation, said liquid fertilizer additives may further compriseone or more biologically active agents and biologics selected from thegroup consisting of a) urease inhibitors, nitrification inhibitors,pesticides, herbicides fungicides(s), and insecticide(s).

In an embodiment, the present invention relates to a method of makingliquid fertilizer additives of biodegradable polymeric and/or oligomericnitrification inhibitors, wherein the method is comprised of utilizing aNAPAOL as the reaction medium for the reaction of aldehyde(s) withcyano-containing nitrification inhibitors that have one or more aldehydereactive groups selected from the group consisting of a) primary amines,b) secondary amines, c) amides, d) thiols, e) hydroxyls and f) phenols.In an embodiment, the composition may further comprise one or morenon-cyano-nitrification inhibitors selected from the group consistingof:

-   -   a) one or more pyrazoles represented by the structure

-   -   Whereas R₂₈=—H, —CH₃, —CH₂CH₃, —NH₂ or —NHCH₃    -   Whereas R₂₉=—H, —OH, —SH, —CONH₂ or —CONHCH₃    -   Whereas R₃₀=—H, —CH₃, —CH₂CH₃, 1'NH₂ or —NHCH₃    -   Whereas R₃₁=—H, —CH₃, —CH₂CH₃, —NH₂ or —NHCH₃    -   b) one or more members selected from the group consisting of        2-amino-4-chloro-6-methyl-pyrimidine, 1,3-benzothiazole-2-thiol,        4-amino-N-1,3-thiazol-2-ylbenzenesulfonamide, thiourea,        2,4-diamino-6-trichloromethyl-5-triazine,        4-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 2,3,        dihydro-2,2-dimethyl-7-benzofuranol methyl-carbamate,

In an embodiment, a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors comprises utilizinga NAPAOL as the reaction medium for the reaction of aldehyde(s) withnon-cyano-containing nitrification inhibitors that have one or morealdehyde reactive groups selected from the group consisting of a)primary amines, b) secondary amines, c) amides, d) thiols, e) hydroxylsand f) phenols. In an embodiment, a liquid fertilizer additive ofbiodegradable polymeric and/or oligomeric nitrification inhibitorscomprises said non-cyano-nitrification inhibitors reacting withparaformaldehyde at a molar ratio of non-cyano-nitrification inhibitorsto formaldehyde compounds of 2:1 to 2.5:1 with NAPAOL as the reactionmedium. In a variation, the composition results in a composition thatcomprises at least 50% or alternatively at least 70% of methylene bisnon-cyano-nitrification inhibitor oligomers. In another variation,methylene bis non-cyano-nitrification inhibitor oligomers are believedto show improvements on performance issues such as lowering atmosphericvolatility and decreasing migration through the soil due to lowmolecular weight and/or water solubility. In a variation, the resultingproduct may also possess nitrification inhibition properties. In avariation, the resulting product may also deliver nitrificationinhibition properties due to the biodegradation of the polymer.

In an embodiment, a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors is comprised ofutilizing a NAPAOL as the reaction medium for the reaction ofaldehyde(s) with non-cyano-containing nitrification inhibitors that haveone or more aldehyde reactive groups selected from the group consistingof a) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols comprise dimethyl pyrazole (DMP) reacting withparaformaldehyde at a molar ratio of DMP to formaldehyde unit of 2:1. Ina variation, the NAPAOL comprises one or more members selected from thegroup consisting of sulfolane and dimethyl sulfoxide as the reactionmedium. In another variation, the composition comprises at least 70% ofa methylene bis DMP oligomer. In another variation, the resulting liquidfertilizer additive possesses lower atmospheric volatility relative tounreacted DMP. In a variation, the NAPAOL is sulfolane.

In an embodiment, a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors is comprised ofutilizing a NAPAOL as the reaction medium for the reaction ofaldehyde(s) with non-cyano-containing nitrification inhibitors that haveone or more aldehyde reactive groups selected from the group consistingof a) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols. In a variation, the method may comprise 1)dissolving the non-cyano-nitrification inhibitor in NAPAOL attemperatures in the range of 30-110° C. and cooling to 40-60° C. andensuring that pH is in the range of 8-10, 2) slowly adding the aldehydeand allowing the exotherm to be controlled either through charge rate orremoving the heat of reaction through a cooling median, 3) slowlyheating the composition to 70-90° C. and waiting for a period of time,(e.g.,1-10 hours) 4) cooling the composition to 40-70° C. and slowlycharging enough of acid catalyst such as but not limited to one or moremembers selected from the group consisting of methane sulfonic acid,sulfuric acid, para-toluene sulfonic acid phosphoric acid and methanephosphonic acid to drop the pH to 5-8 and let mix for an extended periodof time to control the exotherm, 5) slowly heating the composition to90-115° C.

In a variation, after holding the reaction product enumerated above fora period of time, one can elect to place the batch under a vacuum of0.1-100 mm to assist in removing water by-products, driving the reactionto more completion and removing any unreacted aldehyde until residualaldehyde content is <700 ppm and then cooling the batch. In a variation,one can remove oxygen from the reactor before the addition of theformaldehyde. In another variation, one can apply a vacuum to the vesselafter the addition of the acid catalyst to assist in driving thereaction to completion in a shorter period of time. In anothervariation, one can alternate between a hard sparge and vacuum to removeexcess aldehyde.

In an embodiment, a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors is comprised ofutilizing a NAPAOL as the reaction medium for the reaction ofaldehyde(s) with cyano-containing nitrification inhibitors and/ornon-cyano-containing nitrification inhibitors that have one or morealdehyde reactive groups selected from the group consisting of a)primary amines, b) secondary amines, c) amides, d) thiols, e) hydroxylsand f) phenols wherein the NAPAOL comprises one or more members selectedfrom the group consisting of:

-   -   a) dimethyl sulfoxide,    -   b) and dialkyl, diaryl, or alkylaryl sulfoxide(s) having the        formula:

R₉S(O)_(x)R₁₀,

-   -   wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylene group,        an aryl group, or C₁₋₃alkylenearyl group or R₉ and R₁₀ together        with the sulfur to which they are attached form a 4 to 8        membered ring wherein R₉ and R₁₀ together are a C₁₋₆ alkylene        group which optionally contains one or more atoms selected from        the group consisting of O, S, Se, Te, N, and P in the ring and x        is 1 or 2,    -   c) and one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate d) 1-Methyl-2-pyrrolidone, e) one or more        organo phosphorous liquids selected from the group consisting of        hexamethylphosphoramide and one or more trialkylphosphates        selected from the group represented by the formula:

-   -   -   wherein:            -   R₂₂ is alkyl radical —C₁H₃ to —C₆H₁₃            -   R₂₃ is alkyl radical —C₁H₃ to —C₆H₁₃            -   R₂₄ is alkyl radical —C₁H₃ to —C₆H₁₃

    -   f) 1,2-dimethyloxyethane, g) 2-methoxyethyl ether and h)        cyclohexylpyrrolidone,        wherein said nitrification inhibitors that contain one or more        aldehyde reactive groups are selected from the group consisting        of:

    -   a) one or more cyano-containing nitrification inhibitors        selected from the group represented by the structures:

-   -   b) one or more non-cyano-containing nitrification inhibitors        selected from the group consisting of:        -   1) one or more pyrazoles represented by the structure

-   -   -   wherein R₂₈=—H, —CH₃, —CH₂CH₃, —NH₂ or —NHCH₃        -   wherein R₂₉=—H, —OH, —SH, —CONH₂ or —CONHCH₃        -   wherein R₃₀=—H, —CH₃, —CH₂CH₃, —NH₂ or —NHCH₃        -   wherein R₃₁=—H, —CH₃, —CH₂CH₃, —NH₂ or —NHCH₃        -   2) one or more members selected from the group consisting of            2-amino-4-chloro-6-methyl-pyrimidine,            1,3-benzothiazole-2-thiol,            4-amino-N-1,3-thiazol-2-ylbenzenesulfonamide, thiourea,            2,4-diamino-6-trichloromethyl-5-triazine,            4-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 2,3,            dihydro-2,2-dimethyl-7-benzofuranol methyl-carbamate,            wherein the nitrification inhibitors are reacted with said            aldehydes utilizing the NAPAOL as the reaction medium            wherein the one or more aldehydes are selected from the            group consisting of:

    -   methanal, ethanal, propanal, butanal, pentanal, hexanal,        methylethanal, methylpropanal, methylbutanal,        phenylacetaldehyde, benzaldehyde, 2-propenal, 3-oxopropanoic,        2-methyl-3-oxopropanoic acid, 4-oxobutanoic acid, oxoacetic        acid, 5-oxopentanoic acid, 6-oxohexanoic acid, 2-oxopropanal,        cyclohexanal, furfural, methyl esters of 3-oxopropanoic,        2-methyl-3-oxopropanoic acid, 4-oxobutanoic acid, oxoacetic        acid, 5-oxopentanoic acid and 6-oxohexanoic acid, ethandial,        1,3-propanedial, butanedial, pentanedial, phthalaldehyde and        methanethial.

In a variation, a liquid fertilizer additive of biodegradable polymericand/or oligomeric nitrification inhibitors is part of a method comprisedof utilizing NAPAOL as the reaction medium for the reaction ofaldehyde(s) with nitrification inhibitors may further comprise acidcatalyst such as but not limited to one or more members selected fromthe group consisting of methane sulfonic acid, sulfuric acid,para-toluene sulfonic acid, phosphoric acid and methane phosphonic acid.

In another variation, a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors is comprised ofutilizing said NAPAOL as the reaction medium for the reaction of saidaldehyde(s) with said nitrification may further comprise an agent toneutralize the acid catalyst after the reaction is completed such as butnot limited to one or more members selected from the group consisting ofNaOH, NaOCH₃, Na₂CO₃, KOH, K₂CO₃, NH₃ and one or more alkanolaminesselected from the group represented by the structure:

-   -   wherein R⁵ is: C₂H₄OR⁸ or C₃H₆OH    -   wherein R⁶ is: H, C₂H₄OR⁸ or C₃H₆OH    -   wherein R⁷ is: H, C₂H₄OR⁸ or C₃H₆OH    -   wherein R⁸ is: (C₂H₄O)_(g)H    -   and g is an integer between 1-10.

In another variation, the post reaction composition of liquid fertilizeradditive comprising said biodegradable polymeric and/or oligomericnitrification inhibitors is comprised of utilizing a NAPAOL as thereaction medium for the reaction of aldehyde(s) with cyano-containingnitrification inhibitors and/or non-cyano-containing nitrificationinhibitors that have one or more aldehyde reactive groups selected fromthe group consisting of a) primary amines, b) secondary amines, c)amides, d) thiols, e) hydroxyls and f) phenols. In a variation, the postreaction composition may further comprise polar aprotic, aprotic andprotic organo solvent wherein the composition of the non-aqueous liquidorgano solvents may further comprise:

-   -   a) one or more aprotic solvents selected from the group        consisting of 1) one or more polyols capped with acetate or        formate wherein the polyol portion selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol propane,        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and glycerin, 2) one or more        alkylene glycol alkyl ethers acetates selected from the group        consisting of dipropylene glycol methyl ether acetate,        tripropylene glycol methyl ether acetate, and tripropylene        glycol butyl ether acetate and, 3) isophorone, 4) one or more        diesters selected from the group consisting of        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and        dimethyl glutarate, 5) dimethylacetamide, 6)        dimethylformamide, 7) dimethyl-2-imidazolidinone, 8)        1-Methyl-2-pyrrolidone and 9) limonene,    -   b) one or more protic solvents selected from the group        consisting of: 1) an alcohol from the family of C₁₋₁₀        alkanols, 2) one or more polyols selected from the group        consisting of trimethylol propane, trimethylol ethane,        pentaerythritol, sorbitol, sorbitan, glucose, fructose,        galactose, and glycerin, 3) one or more poly(C₁₋₁₀ alkylene)        glycols represented by the structure:

H(C_(t)H_(u))_(v)OH

-   -   -   t is an integer: 1-10        -   u is an integer: 2-20        -   and        -   v is an integer: 1-20,

    -   4) one or more alkylene glycols selected from the group        consisting of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, and butylene glycol, 5) isopropylidene        glycerol 6) one or more alkylene glycol alkyl ethers selected        from the group represented by the structure:

-   -   -   wherein R¹ is: CH₃, C₂H₅, C₃H₇ or C₄H₉        -   wherein R² is: H or the structure

-   -   -   wherein R³ is: H or CH₃        -   wherein R⁴ is H and CH₃            -   and f is an integer between 1 and 15

    -   7) one or more alkyl lactates selected from the group consisting        of ethyl, propyl and butyl lactate, 8) one or more alkanolamines        selected from the group represented by the structure:

-   -   -   where R⁵ is: C₂H₄OR⁸ or C₃H₆OH        -   where R⁶ is: H, C₂H₄OR⁸ or C₃H₆OH        -   where R⁷ is: H, C₂H₄OR⁸ or C₃H₆OH        -   where R⁸ is: (C₂H₄O)_(g)H        -   and g is an integer between 1-10

    -   and 9) glycerol carbonate,

    -   c) and one or more polar aprotic solvents selected from the        group consisting of        -   1) dimethyl sulfoxide        -   2) and dialkyl, diaryl, or alkylaryl sulfoxide(s) having the            formula:

R₉S(O)_(x)R₁₀

-   -   -   -   wherein R₉ and R₁₀ are each independently a C₁₋₆                alkylene group, an aryl group, or C₁₋₃alkylenearyl group                or R₉ and R₁₀ together with the sulfur to which they are                attached form a 4 to 8 membered ring            -   wherein R₉ and R₁₀ together are a C₁₋₆ alkylene group                which optionally contains one or more atoms selected                from the group consisting of O, S, Se, Te, N, and P in                the ring and x is 1 or 2, and optionally further                comprising

        -   3) one or more alkylene carbonates selected from the group            consisting of ethylene carbonate, propylene carbonate and            butylene carbonate 4) 1-Methyl-2-pyrrolidone, 5) one or more            organo phosphorous liquids selected from the group            consisting of hexamethylphosphoramide and one or more            trialkylphosphates selected from the group represented by            the formula.

-   -   -   -   wherein:                -   R₂₂ is alkyl radical —C₁H₃ to —C₆H₁₃                -   R₂₃ is alkyl radical —C₁H₃ to —C₆H₁₃                -   R₂₄ is alkyl radical —C₁H₃ to —C₆H₁₃            -   6) 1,2-dimethyloxyethane, 7) 2-methoxyethyl ether and 8)                cyclohexylpyrrolidone

In an embodiment, said non-aqueous organo liquid solvents can be addedto improve the properties of said liquid fertilizer additives such asbut not limited to hydrophobicity, viscosity and cold weatherflowability and/or the properties of the treated nitrogen source such asbut not limited to water resistance, clumping of solid nitrogen sourcesand solubility in liquid/molten nitrogen sources.

In another variation, the composition may further comprise one or moremembers selected from the group consisting of:

-   -   a food coloring or dye that may be used to improve the visual        evidence of complete coverage and serve as a visual marker,    -   scents or masking agents to improve the odor of the        formulations,    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules;    -   buffering agents    -   flow modifiers, silicas and hydrophobized silicas and    -   catalyst(s) to improve reaction completion.

In another variation, the composition may further comprise one or moremembers selected from the group consisting of: a) one or morebiologically active agents and b) biologics wherein the biologicallyactive agents and biologics may possess one or more properties selectedfrom the group consisting of a) urease inhibitors, nitrificationinhibitors, pesticides, herbicides fungicides(s) and insecticide(s)

In an embodiment, a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors is comprised ofutilizing a NAPAOL as the reaction medium for the reaction ofaldehyde(s) with cyano- and/or non-cyano-containing nitrificationinhibitors that have one or more aldehyde reactive groups selected fromthe group consisting of a) primary amines, b) secondary amines, c)amides, d) thiols, e) hydroxyls and f) phenols may further comprise oneor more members selected from the group consisting of: a) one of morebiologically active agents and b) one or more biologics wherein thebiologically active agents and biologics may possess one or moreproperties selected from the group consisting of urease inhibitors,nitrification inhibitor(s), pesticide(s), herbicide(s), fungicides(s),and insecticide(s). In a variation, the use of a liquid fertilizeradditive of biodegradable polymeric and/or oligomeric nitrificationinhibitors will result in lower dissolution of these biologically activeagents that are encapsulated within the hydrophobic film therebyimproving performance by increasing the length of time thesebiologically active agents and biologics are available.

In an embodiment, a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors is comprised ofutilizing a NAPAOL as the reaction medium for the reaction ofaldehyde(s) with cyano-containing nitrification inhibitors and/ornon-cyano-containing nitrification inhibitors that have one or morealdehyde reactive groups selected from the group consisting of a)primary amines, b) secondary amines, c) amides, d) thiols, e) hydroxylsand f) phenols may further comprise one or more urease inhibitorsselected from the group consisting of aliphatic phosphoric triamide,phosphoramides and N-alkyl thiophosphoric triamides,(aminomethyl)phosphinic acids and their salts and aminomethyl(alkylaminomethyl)phosphinic acids and their salts. In a variation theurease inhibitor is N-(n-butyl) thiophosphoric triamide.

In an embodiment, a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors is comprised ofutilizing a NAPAOL as the reaction medium for the reaction ofaldehyde(s) with cyano-containing nitrification inhibitors and/ornon-cyano-containing nitrification inhibitors that have one or morealdehyde reactive groups selected from the group consisting of a)primary amines, b) secondary amines, c) amides, d) thiols, e) hydroxylsand f) phenols may further comprise one or more nitrification inhibitorsselected from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4-6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD),thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate,dimethylpyrazole organic and inorganic salts and2-amino-4-chloro-6-methylpyrimidine In a variation the nitrificationinhibitor comprises dicyandiamide.

In an embodiment a liquid fertilizer additive of biodegradable polymericand/or oligomeric nitrification inhibitors is comprised of utilizing aNAPAOL as the reaction medium for the reaction of aldehyde(s) withcyano-containing nitrification inhibitors and/or non-cyano-containingnitrification inhibitors that have one or more aldehyde reactive groupsselected from the group consisting of a) primary amines, b) secondaryamines, c) amides, d) thiols, e) hydroxyls and f) phenols may furthercomprise one or more nitrification inhibitors selected from the groupconsisting of 2-chloro-6-trichloromethyl)pyridine,4-amino-1,2,4-6-triazole-HCl, 2,4-diamino-6-trichloromethyltriazineCL-1580, dicyandiamide (DCD), thiourea, 1-mercapto-1,2,4-triazole,ammonium thiosulfate, dimethylpyrazole organic and inorganic salts and2-amino-4-chloro-6-methylpyrimidine and one or more urease inhibitorsselected from the group consisting of aliphatic phosphoric triamide,phosphoramides and N-alkyl thiophosphoric triamides,(aminomethyl)phosphinic acids and their salts and aminomethyl(alkylaminomethyl) phosphinic acids and their salts.

In an embodiment a liquid fertilizer additive of biodegradable polymericand/or oligomeric nitrification inhibitors is comprised of utilizing aNAPAOL as the reaction medium for the reaction of aldehyde(s) withcyano-containing nitrification inhibitors and/or non-cyano-containingnitrification inhibitors that have one or more aldehyde reactive groupsselected from the group consisting of a) primary amines, b) secondaryamines, c) amides, d) thiols, e) hydroxyls and f) phenols may furthercomprise one or more biologics selected from the group consisting of

-   -   a) one or more Bacillus biologics selected from the group        consisting of        -   1) Bacillus mucilaginosas        -   2) Bacillus Subtilus        -   3) Lactobacillus acidophilus        -   4) Baciillus amylofliquifaciens        -   5) Bacillus itcheniformis        -   6) Bacillus megaterium        -   7) Bacillus pumilus        -   8) Bacillus megaterium        -   9) Bacillus pumilus        -   10) Bacillus circulans        -   11) Bacillus globisporus        -   12) Bacillus firmus        -   13) Bacillus thuringiensis galleriae        -   14) Bacillus thuringiensis kurstaki        -   15) Bacillus cereus        -   16) Bacillus globisporus        -   17) Bacillus amyloliquefaciens        -   18) Bacillus thuringiensis galleriae        -   19) Bacillus thuringiensis kurstaki        -   20) Bacillus mycoide isolate        -   21) Bacillus aryabhattai        -   22) B. flexus        -   23) B. nealsonii        -   24) Bacillus sphaericus        -   25) B. vallismortis    -   b) Rhizobium    -   c) Bradyrhiwbium species    -   d) Bradyrhiwbium japonicum    -   e) Rhizobium meliloti    -   f) One or more Azospirillum biologics selected from the group        consisting of        -   1) Azospirillum lipoferum        -   2) Azospirillum brasilense        -   3) Azospirillum amazonense        -   4) Azospirillum halopreaferens    -   5) Azospirillum irankense    -   g) One or more Azobacter and Gluconacetobacter biologics        selected from the group consisting of        -   1) Azotobacter agilis        -   2) Azotobacter armeniacus        -   3) Azotobacter sp. AR        -   4) Azotobacter beijerinckii        -   5) Azotobacter chroococcum        -   6) Azotobacter sp. DCU26        -   7) Azotobacter sp. FA8        -   8) Azotobacter nigricans        -   9) Azotobacter paspali        -   10) Azotobacter salinestris        -   11) Azotobacter tropicalis        -   12) Azotobacter vinelandii    -   h) Phosphobacteria    -   i) Cyanobacteria    -   j) Herbaspirillum    -   k) Burkholderia,    -   l) Pseudomonas    -   m) Gluconacetobacter    -   n) Enterobacter    -   o) Klebsiella    -   p) Burkholderia    -   q) Laccaria bicolor    -   r) Glomus imraradices timanita    -   s) Actinomyces    -   t) Penicillium    -   u) Mesorhizobiwn cicero    -   v) Reynoutria sachalinensis    -   w) One or more insecticidal or insect repellent microbial        species and strains selected from the group consisting of:        Telenomus podisi, Baculovirus anticarsia, Trichogramma        pretiosum, Trichogramma gallai, Chromobacterium subtsugae,        Trichoderma fertile, Beauveria bassiana, Beauveria bassiana,        Beauveria bassiana, Paecilomyces jknwsoroseu, Trichoderma        harzianum, Verticillium lecanii, lsarfofumosarosea Lecanicillium        muscarium, Streptomyces microflavus, Muscodor albus,    -   x) one or more nematodal microbial species and strains selected        from the group consisting of: Myrothecium verrucaria, Pasteuria        species, Pasteuria Metarhizium species, Flavobacteriwn species        and    -   y) one or more antifungal, antimicrobial and/or plant growth        promoting microbial species and strains selected from a group        consisting of: Gliocladium species, Pseudomonas species (e.g.        Pseudomonas fluorescens, Pseudomonas fluorescens. putida and P.        chlororaphis), Pseudomonasfluorescens VP5, Pseudomonas        diazotrophicus, Enterobacter cloacae, Trichodema species,        Trichoderma virens, Trichoderma atroviride strains, Coniothyrium        minitans, Gliocladium species, Gliacladium virens, Gliacladium        roseum, Trichodemw harzianum species.

In an embodiment, these new liquid fertilizer additives can be added toa nitrogen source through methods comprising one or more applicationtechniques selected from the group consisting of:

-   -   a. coating a nitrogen source particle with said liquid        fertilizer additives utilizing spraying, metering or slowly        pouring onto a nitrogen source that is in a temperature range of        −20° C. to 100° C. In a variation the mixing of the materials        may be accomplished in a simple mixing tank mixing materials        prior to use, using a metering system to inject materials        simultaneously, or mixing via a spray injection system. In        another variation, the mixture can be mixed in any common mixing        tank, blenders and tumblers or on a conveyer belt. In another        variation, the metering of all ingredients can be based on a        weight, it may also be on a volumetric basis,    -   b. generating during the process a nitrogen source particle,        granule and/or prill in which the liquid formulation can be        added directly into the molten nitrogen source before formation        of a particle, granule or a prill and/or sprayed into the        prilling tower when molten nitrogen source is released from the        top of prilling tower and the falling liquid nitrogen source is        crystallized by air in the tower,    -   c. dissolving liquid fertilizer additive into aqueous liquid        fertilizers and    -   d. incorporating said liquid fertilizer additives into        non-aqueous liquid nitrogen sources such as pressurized        anhydrous ammonia gas.

In a variation, these compositions can be sprayed directly on the soiland/or on natural fertilizers such as manure or compost.

In an embodiment, the usage rates of these new liquid formulations witha nitrogen source is dependent on the application technique, the weightor volume of the nitrogen source applied per acre of soil to be treated,the nitrification inhibitor type, the concentration of polymer bound andfree nitrification inhibitors present in the liquid formulation'scomposition. In a variation, if the application technique is theaddition of said liquid fertilizer additives to a liquid/molten nitrogensource, the usage rate will be dependent on the solubility and impact ofthe desired granule/prill properties.

In a variation, higher levels of total nitrification inhibitors, whichare defined as polymer bound and free, can be applied to the soildirectly or as a liquid fertilizer additive to natural and manmadenitrogen sources. Moreover, due to the slow release of nitrificationinhibitors through the biodegradation of the polymer backbone and themaintenance of an effective level of free nitrification inhibitors, thenitrogen source is made more effective in providing nutrients for plantgrowth over an extended period of time. In a variation, a liquidfertilizer additive of biodegradable polymeric and/or oligomericnitrification inhibitors is comprised of utilizing a NAPAOL as thereaction medium for the reaction of aldehyde(s) with cyano-containingnitrification inhibitors and/or non-cyano-containing nitrificationinhibitors that have one or more aldehyde reactive groups selected fromthe group consisting of a) primary amines, b) secondary amines, c)amides, d) thiols, e) hydroxyls and f) phenols may have low percentagesof 20-30% of a NAPAOL resulting in lower negative impact of a nitrogensource particles' physical properties such as but not limited to a lowhardness index. In a variation, a low hardness index of a particlenegatively impacts storage, packaging, blending and distribution. Inanother variation, low percent composition of NAPAOL in a liquidfertilizer additive may be achieved by running the first reactionprocess at lower temperatures of 60-80° C. for a longer period of time(e.g. 4-12 hours).

In another variation, low percent composition of NAPAOL in a liquidfertilizer additive may be achieved by running the second reactionprocess at a lower vacuum (e.g. 0.01-1 mm), increasing the temperatureafter the second reaction has been completed and any acid catalyst hasbeen neutralized (e.g. 90-120° C.) stripping out NAPAOL to desiredlevels.

In another variation, a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors is comprised ofutilizing a NAPAOL as the reaction medium for the reaction ofaldehyde(s) with cyano-containing nitrification inhibitors and/ornon-cyano-containing nitrification inhibitors that have one or morealdehyde reactive groups selected from the group consisting of a)primary amines, b) secondary amines, c) amides, d) thiols, e) hydroxylsand f) phenols may be added to molten nitrogen sources at elevatedtemperatures (e.g. 80-140° C.) to lower said liquid fertilizeradditive's viscosity and aide in ensuring a homogeneous distributionwithin the molten nitrogen source.

In an embodiment, the composition of a fertilizer comprises liquidfertilizer additives of biodegradable polymeric and/or oligomericnitrification inhibitors that are comprised of utilizing a NAPAOL as thereaction medium for the reaction of aldehyde(s) with cyano-containingnitrification inhibitors and/or non-cyano-containing nitrificationinhibitors that have one or more aldehyde reactive groups selected fromthe group consisting of a) primary amines, b) secondary amines, c)amides, d) thiols, e) hydroxyls and f) phenols and one or more nitrogensources selected from a group consisting of urea, urea formaldehydepolymer, treated urea. In an embodiment, the treated urea is defined asa composition comprising a urea and biologically active agents and/orbiologics added either through a coating application or added to theurea during the urea production process either in the melt portion ordeposited to the urea during the formation of the urea granule when theurea is still hot. In a variation, a liquid fertilizer additives ofbiodegradable polymeric and/or oligomeric nitrification inhibitorscomprise 0.05-10% of the fertilizer composition. In another variation,the NAPAOL comprises 0.01-9.5% of the fertilizer composition.

In an embodiment, one can coat a granule of treated nitrogen source witha liquid fertilizer additive of biodegradable polymeric and/oroligomeric nitrification inhibitors that is comprised of utilizing aNAPAOL as the reaction medium for the reaction of aldehyde(s) withcyano-containing nitrification inhibitors and/or non-cyano-containingnitrification inhibitors that have one or more aldehyde reactive groupsselected from the group consisting of a) primary amines, b) secondaryamines, c) amides, d) thiols, e) hydroxyls and f) phenols. A treatednitrogen source is defined as a composition comprising a nitrogen sourceand biologically active agents and/or biologics added either through acoating application or added to the nitrogen source during the nitrogensource's production process either in the melt portion or applied to thenitrogen source during the formation of the nitrogen source's granule.

In a variation, the nitrogen sources and/or the treated nitrogen sourcescan be mixed with other fertilizer components and then the liquidfertilizer additives of biodegradable polymeric and/or oligomericnitrification inhibitors comprised of utilizing a NAPAOL as the reactionmedium for the reaction of aldehyde(s) with cyano-containingnitrification inhibitors and/or non-cyano-containing nitrificationinhibitors that have one or more aldehyde reactive groups selected fromthe group consisting of a) primary amines, b) secondary amines, c)amides, d) thiols, e) hydroxyls and f) phenols can be applied. This willimpart slower dissolution of these fertilizer components and nitrogenand/or treated nitrogen sources into water because they have beenencapsulated within the hydrophobic film. In an embodiment said liquidfertilizer additives will provide free and polymer bound nitrificationinhibition, thereby improving performance in providing nutrients forplant growth over an extended period of time.

In one embodiment, a fertilizer comprises a) a liquid fertilizeradditive of biodegradable polymeric and/or oligomeric nitrificationinhibitors that is comprised of utilizing a NAPAOL as the reactionmedium for the reaction of aldehyde(s) with cyano-containingnitrification inhibitors and/or non-cyano-containing nitrificationinhibitors that have one or more aldehyde reactive groups selected fromthe group consisting of 1) primary and secondary amines, 2) amides, 3)thiols, 4) hydroxyls and 5) phenols and urea. In a variation, saidliquid fertilizer additives deliver a more hydrophobic coating of freeand polymer bound nitrification inhibitors making the urea moreeffective in providing nutrients for plant growth over an extendedperiod of time.

In an embodiment, the composition of a fertilizer comprises urea and aliquid fertilizer additives of biodegradable polymeric and/or oligomericnitrification inhibitors that is comprised of utilizing a NAPAOL as thereaction medium for the reaction of aldehyde(s) with cyano-containingnitrification inhibitors and/or non-cyano-containing nitrificationinhibitors that have one or more aldehyde reactive groups selected fromthe group consisting of a) primary amines, b) secondary amines, c)amides, d) thiols, e) hydroxyls and f) phenols. In another embodiment,the composition of a fertilizer may further comprise one or more membersselected from the group consisting of: a) one of more biologicallyactive agents and b) one or more biologics wherein the biologicallyactive agents and biologics may possess one or more properties selectedfrom the group consisting of urease inhibitors, nitrificationinhibitor(s), pesticide(s), herbicide(s), fungicides(s), andinsecticide(s). In a variation, when the fertilizer is applied tocropland and turf, the new liquid fertilizer additive composition makesthe urea more effective in providing nutrients for plant growth over anextended period of time.

In an embodiment, a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors is comprised ofutilizing a NAPAOL as the reaction medium for the reaction ofaldehyde(s) with cyano-containing nitrification inhibitors and/ornon-cyano-containing nitrification inhibitors that have one or morealdehyde reactive groups selected from the group consisting of a)primary amines, b) secondary amines, c) amides, d) thiols, e) hydroxylsand f) phenols comprises DCD. In a variation, the NAPAOL comprisesdimethyl sulfoxide.

In an embodiment, the composition of said liquid fertilizer additivescomprises 5-80% the reaction product of aldehyde(s) reacted withcyano-containing nitrification inhibitors and/or non-cyano-containingnitrification inhibitors that have one or more aldehyde reactive groupsselected from the group consisting of a) primary amines, b) secondaryamines, c) amides, d) thiols, e) hydroxyls and f) phenols and 95-20% ofa NAPAOL. In a variation, the composition may further comprise 0.05 to50% of biologically active agents and/or biologics.

In an embodiment, a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors comprises utilizinga NAPAOL as the reaction medium for the reaction of aldehyde(s) withcyano-containing nitrification inhibitors and/or non-cyano-containingnitrification inhibitors that have one or more aldehyde reactive groupsselected from the group consisting of a) primary amines, b) secondaryamines, c) amides, d) thiols, e) hydroxyls and f) phenols. In avariation, said liquid fertilizer additive composition may furthercomprise one or more organo polyorganic acids and/or their salts. In avariation, the composition of the polyacid one or more members selectedfrom the group consisting of a monomer homopolymer, a copolymer and/or aterpolymer or one or more members selected from a group consisting of:

-   -   aspartic acid    -   glutamic acid    -   maleic anhydride    -   itaconic anhydride    -   citraconic anhydride    -   citric acid; or    -   acrylic acid;        wherein the organo polyorganic acids are present in an amount        that is about 5-50% of the total composition. In a variation,        the cation of the salts of the polyacids comprise one or more        metals selected from the group consisting of Na, K, Mg, Ca, Fe,        Zn, Mn, Cu, Co, Mo, or Ni and one or more organoamine selected        from the group consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri        C₁₋₆ amine, mono ethanol amine, diethanol amine, triethanol        amine, monoisopropyl amine, diisopropyl amine, triisopropyl        amine, diethyl amine, diethylene triamine, triethyl tetraamine,        tetraethyl pentamine.

In another variation, the composition comprised of said liquidfertilizer additives and said polyacids and/or their salts can beapplied to natural and manmade nitrogen sources utilizing one or moreapplication techniques selected from the group consisting of:

-   -   a. coating a nitrogen source particle with said liquid        fertilizer additives utilizing spraying, metering or slowly        pouring onto a nitrogen source that is in a temperature range of        −20° C. to 100° C. In a variation the mixing of the materials        may be accomplished in a simple mixing tank mixing materials        prior to use, using a metering system to inject materials        simultaneously, or mixing via a spray injection system. In        another variation, the mixture can be mixed in any common mixing        tank, blenders and tumblers or on a conveyer belt. In another        variation, the metering of all ingredients can be based on a        weight, it may also be based on a volumetric basis,    -   b. incorporating during the process a nitrogen source particle,        granule and/or prill in which the liquid formulation can be        added directly into the molten nitrogen source before formation        of a particle, granule or a prill and/or sprayed into the        prilling tower when molten nitrogen source is released from the        top of prilling tower and the falling liquid nitrogen source is        crystallized by air in the tower,    -   c. dissolving liquid fertilizer additive into aqueous liquid        fertilizers and    -   d. incorporating said liquid fertilizer additives into        non-aqueous liquid nitrogen sources such as pressurized        anhydrous ammonia gas.

In a variation, said liquid formulations can be sprayed directly ontothe soil and onto natural fertilizers such as manure.

In another variation, application of the composition comprised of saidliquid fertilizer additives and said polyacids and/or their salts willimprove the effectiveness of the treated fertilizer due to the slowrelease of nitrification inhibitors through the biodegradation of thepolymer backbone resulting in the maintenance of an effective level offree nitrification inhibitors. In another variation, the presence of theorgano polyacids and/or their salts will assist in freeing soil boundphosphates and micronutrients, provide a micronutrient transport andmoisture protection in the root zone when injected subsurface inapplications such as anhydrous ammonia. In another variation, the organopolyacids in an acid/anhydride/imide configuration can provide nitrogenconservation to the nitrogen source making the fertilizer more effectivein providing nutrients for plant growth over an extended period of time.

In an embodiment, the capability of the NAPAOL to also serve as anon-aqueous organo solvent delivery system (abbreviated as NOSDS) allowsthe application of the liquid composition to nitrogen sources thatutilize moisture sensitive application methods. It has been learned thatliquid biodegradable polymeric and/or oligomeric nitrificationinhibitors comprised of utilizing a non-aqueous polar, aprotic organoliquid (NAPAOL) as the reaction medium for the reaction of aldehyde(s)with cyano-containing nitrification inhibitors that have one or morealdehyde reactive groups selected from the group consisting of a)primary amines, b) secondary amines, c) amides, d) thiols, e) hydroxylsand f) phenols assist to conserve the cyano-group. In a variation, theliquid biodegradable polymeric and/or oligomeric nitrificationinhibitors is comprised of utilizing a non-aqueous polar, aprotic organoliquid (NAPAOL) as the reaction medium for the reaction of aldehyde(s)with nitrification inhibitors that have one or more aldehyde reactivegroups selected from the group consisting of a) primary amines, b)secondary amines, c) amides, d) thiols, e) hydroxyls and f) phenols canpossess higher levels of polymer bound and free nitrification inhibitorsversus products utilizing a NAPAOL to make solutions of freenitrification inhibitors. In a variation, it has been learned thatutilizing a NAPAOL as the reaction medium results in highercompositional weight percent of said liquid biodegradable polymericand/or oligomeric nitrification inhibitors versus those produced in anaqueous medium nitrification inhibitors.

In an embodiment, the compositions and methods of making a liquidfertilizer additive of biodegradable polymeric and/or oligomericnitrification inhibitors are comprised of utilizing a non-aqueous polar,aprotic organo liquid (NAPAOL) as the reaction medium for the reactionof aldehyde(s) with cyano-containing nitrification inhibitors that haveone or more aldehyde reactive groups selected from the group consistingof a) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols, wherein said liquid fertilizer additive isapplied to the soil directly either before or after the application of anitrogen source or in a composition with a nitrogen source inhibits theloss of the nitrogen source's nitrogen caused by the microbial processtermed nitrification. In a variation, the method of making a liquidfertilizer additive of biodegradable polymeric and/or oligomericnitrification inhibitors wherein the process parameters are optimized toconserve the cyano group of the nitrification inhibitor preventing itfrom being converted to diaminomethylene urea comprise a) controlling pHof the reaction, b) utilization of a NAPAOL as the reaction medium, c)using a two-step reaction strategy wherein the first reactionincorporates an aldehyde with a cyano-containing nitrification inhibitorthat have one or more aldehyde reactive groups selected from the groupconsisting of i) primary amines, ii) secondary amines, iii) amides, iv)thiols, v) hydroxyls and vi) phenol to form methylol groups and thesecond is the reaction of the methylol group with an aldehyde reactivegroup of the nitrification inhibitor to form polymeric and/or oligomericnitrification inhibitors and d) removing water during the secondreaction resulting in improved nitrification inhibition properties.

In an embodiment, a liquid fertilizer additive comprised ofbiodegradable polymeric and/or oligomeric nitrification inhibitorsresulting from the reaction of aldehyde(s) with cyano-containingnitrification inhibitors that have one or more aldehyde reactive groupsselected from the group consisting of a) primary amines, b) secondaryamines, c) amides, d) thiols, e) hydroxyls and f) phenols utilizing aNAPAOL as the reaction medium has improved nitrification inhibitionproperties when compared to its monomeric form.

In an embodiment, there is a maximum polymer weight of biodegradablepolymeric and/or oligomeric nitrification inhibitors resulting from thereaction of aldehyde(s) with cyano-containing nitrification inhibitorsthat have one or more aldehyde reactive groups selected from the groupconsisting of a) primary amines, b) secondary amines, c) amides, d)thiols, e) hydroxyls and f) phenols utilizing a NAPAOL as the reactionmedium wherein the viscosity, water solubility and biodegradabilityproperties of the liquid fertilizer additive negatively impactnitrification inhibition.

In an embodiment, a liquid fertilizer additive comprised of a)biodegradable polymeric and/or oligomeric nitrification inhibitorsresulting from the reaction of aldehyde(s) with cyano-containingnitrification inhibitors that have one or more aldehyde reactive groupsselected from the group consisting of i) primary amines, ii) secondaryamines, iii) amides, iv) thiols, v) hydroxyls and vi) phenolsb)utilizing a NAPAOL as the reaction medium and c) one or morenitrification inhibitors selected from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4-6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD),thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate,dimethylpyrazole and/or its organic and inorganic salts and2-amino-4-chloro-6-methylpyrimidine has improved nitrificationinhibition properties when compared to the monomeric form of the addednitrification inhibitors. In a variation, the composition can furthercomprise protic and aprotic solvents.

In an embodiment, liquid fertilizer additives comprises:

-   -   1) a NAPAOL,    -   2) aldehydes    -   3) one or more nitrification inhibitors selected from the group        consisting of 2-chloro-6-trichloromethyl)pyridine,        4-amino-1,2,4-6-triazole-HCl,        2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide        (DCD), thiourea, 1-mercapto-1,2,4-triazole, ammonium        thiosulfate, dimethylpyrazole and/or its organic and inorganic        salts and 2-amino-4-chloro-6-methylpyrimidine,    -   4) one or more dicyandiamide—formaldehyde adducts selected from        the group consisting of the following structures:

wherein the NAPAOL comprises one or more members selected from the groupconsisting of:

-   -   a) dimethyl sulfoxide,    -   b) and dialkyl, diaryl, or alkylaryl sulfoxide(s) having the        formula:

R₉S(O)_(x)R₁₀,

-   -   wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylene group,        an aryl group, or C₁₋₃alkylenearyl group or R₉ and R₁₀ together        with the sulfur to which they are attached form a 4 to 8        membered ring wherein R₉ and R₁₀ together are a C₁₋₆ alkylene        group which optionally contains one or more atoms selected from        the group consisting of O, S, Se, Te, N, and P in the ring and x        is 1 or 2,    -   c) and one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate d) 1-Methyl-2-pyrrolidone, e) one or more        organo phosphorous liquids selected from the group consisting of        hexamethylphosphoramide and one or more trialkylphosphates        selected from the group represented by the formula:

-   -   wherein:        -   R₂₂ is alkyl radical —C₁H₃ to —C₆H₁₃        -   R₂₃ is alkyl radical —C₁H₃ to —C₆H₁₃        -   R₂₄ is alkyl radical —C₁H₃ to —C₆H₁₃    -   f) 1,2-dimethyloxyethane, g) 2-methoxyethyl ether and h)        cyclohexylpyrrolidone, wherein the one or more aldehydes are        selected from the group consisting of:        -   methanal, ethanal, propanal, butanal, pentanal, hexanal,            methylethanal, methylpropanal, methylbutanal,            phenylacetaldehyde, benzaldehyde, 2-propenal,            3-oxopropanoic, 2-methyl-3-oxopropanoic acid, 4-oxobutanoic            acid, oxoacetic acid, 5-oxopentanoic acid, 6-oxohexanoic            acid, 2-oxopropanal, cyclohexanal, furfural, methyl esters            of 3-oxopropanoic, 2-methyl-3-oxopropanoic acid,            4-oxobutanoic acid, oxoacetic acid, 5-oxopentanoic acid and            6-oxohexanoic acid, ethandial, 1,3-propanedial, butanedial,            pentanedial, phthalaldehyde and methanethial,            wherein the said liquid fertilizer composition can added to            molten urea and/or ammonia resulting in an insitu            modification of urea and/or ammonia within the urea            manufacturing process,

and wherein the NAPAOL would have urea solubilizing properties ensuringa more homogeneous distribution of nitrification inhibitors within theurea.

In a variation R₃₂-R₄₁ further comprise one or more membersindependently selected from the group consisting of: CH₂—Z,

-   -   wherein Z=DCD or a DCD-formaldehyde adduct.

In a variation, the NAPAOL is dimethyl sulfoxide.

In an embodiment, a method of making liquid fertilizer additives ofbiodegradable polymeric and/or oligomeric nitrification inhibitorscomprises utilizing a NAPAOL as the reaction medium for the reaction ofaldehyde(s) with cyano-containing nitrification inhibitors that have oneor more aldehyde reactive groups selected from the group consisting ofa) primary amines, b) secondary amines, c) amides, d) thiols, e)hydroxyls and f) phenols is designed such that the aldehyde is reactedto its methylol function versus continued reaction with formaldehydereactive groups crosslinking to the methylene function wherein the molarratio is set to ensure that the aldehyde to aldehyde reactive groupsratio available in said cyano-containing nitrification inhibitors. In avariation, the methylol function can be capped to an alkoxy groupcomprising of —CH3 to —C4H9 alkyl radical

—NI—CH2-OH vs NI—CH2-NI

In an embodiment, the following drawings of dicyandiamide reacted withformaldehyde would represent desired structure formed versuscrosslinking to the methylene function:

In an embodiment, the molar ratio of said aldehyde to saidcyano-containing nitrification inhibitors' aldehyde reactive groupscomprise 1:1 to 4:1. In a variation, the molar ratio of said aldehyde tosaid cyano-containing nitrification inhibitors is set with an excess ofaldehyde groups to ensure reactive methylol groups present after thereaction is terminated. In a variation, the ratio of aldehyde groups toaldehyde reactive groups further comprise >4:1

In an embodiment, the reaction parameters and molar ratios can be setsuch that the formation of methylene bridges is limited resulting in aliquid fertilizer additive-AMC (aldehyde-methylol containing) comprisingunreacted aldehyde, nitrification inhibitors and nitrificationinhibitors-aldehyde reaction product containing methylol functionswherein the method to make may comprise 1) dissolving the nitrificationinhibitor in NAPAOL at temperatures in the range of 20-110° C. andcooling to 20-60° C. and ensuring that pH is in the range of 8-10, 2)slowly adding the aldehyde and allowing the exotherm to be controlledeither through charge rate or removing the heat of reaction through acooling medium while holding the temperature at 40-60° C., 3) Heatvessel contents at 60-100° C. for 2 to 18 hours and then cool to <40° C.In a variation, the nitrification inhibitor is dissolved in a NAPAOL at20-80° C. and the aldehyde is subsequently dispersed into the dissolvedand/or dispersed nitrification inhibitor wherein the composition is aliquid fertilizer additive-A (aldehyde).

In a variation, the reaction parameters and molar ratios can be set suchthat the formation of methylene bridges is limited resulting in a liquidfertilizer additive-AMC comprising unreacted aldehyde, nitrificationinhibitors and/or nitrification inhibitors-aldehyde reaction productcontaining methylol functions wherein the method to make may comprise 1)charging the nitrification inhibitor and aldehyde in a NAPAOL attemperatures in the range of 20-40° C. and then removing oxygen from thevessel's headspace, 2) slowly heat vessel contents to 60-100° C., 3)Hold at 60-100° C. for 2 to 18 hours and then cool to <40° C.

In an embodiment, a liquid fertilizer additive-AMC and or a liquidfertilizer-A can be added to molten urea, molten urea/ammonia andammonia to disperse into the nitrogen source and react with the urea,urea and ammonia and ammonia incorporating nitrification inhibitors intothe backbone of a urea-formaldehyde and/or a urea-ammonia-formaldehydepolymer with even distribution of the nitrification inhibitor throughoutthe resulting polymer.

The reaction parameters and molar ratios can be set such that theformation of methylene bridges is favored, the said nitrificationinhibitors-aldehyde adduct can be further reacted with an aldehyderesulting in a liquid fertilizer additive comprising unreacted aldehyde,nitrification inhibitors, nitrification inhibitors-aldehyde reactionproduct and nitrification inhibitors-aldehyde reaction productcontaining methylol functions wherein the method to make comprises oneor more of the following steps selected from the group consisting of:

-   -   a) charging said aldehydes, said nitrification inhibitors and        said NAPAOL to reaction vessel and start mixing,    -   b) heating contents of the vessel to 50-90° C. and hold at        temperature for 1-7 hours,    -   c) cooling to 40-60° C., charging an acid catalyst such as but        not limited to one or more members selected from the group        consisting of methane sulfonic acid, sulfuric acid, para-toluene        sulfonic acid phosphoric acid and methane phosphonic acid,        placing reaction vessel under a vacuum of 0.5-50 mm, increasing        temperature to 90-120° C. and hold under vacuum and at        temperature until distillation ceases, cool to 40° C.,    -   d) adjust pH to 8-10 with 10% NaOH or KOH and then 10-200% more        aldehyde calculated on the amount of initial aldehyde charged,    -   e) Heat contents of vessel to 70-80° C. and hold for 1-5 hours,    -   f) Optional to cool batch below 40° C. for storage,

In a variation, the material from step “d” can be added as is to moltenurea, molten urea/ammonia and ammonia to disperse into the nitrogensource and react with the urea, urea and ammonia and ammoniaincorporating blocks of nitrification inhibitors into the backbone of aurea-formaldehyde and/or a urea-ammonia-formaldehyde polymer. In anothervariation, the polymeric/oligomeric nitrification inhibitor comprisesdicyandiamide wherein when added to a molten nitrogen source can formhydrophobic DCD blocks creating zones of water resistance within theresulting urea particle,

In another variation, the material from step “e” can be added as is tomolten urea, molten urea/ammonia and ammonia to disperse into thenitrogen source and react with the urea, urea and ammonia and ammoniaincorporating blocks of nitrification inhibitors into the backbone of aurea-formaldehyde and/or a urea-ammonia-formaldehyde polymer. In anothervariation, the polymeric/oligomeric nitrification inhibitor comprisesdicyandiamide segments wherein when added to a molten nitrogen sourcecan form hydrophobic DCD blocks creating zones of water resistancewithin the resulting urea particle.

In an embodiment, the nitrogen source ferilizer particles formed fromthe urea and/or urea-ammonia molten liquid containing the insitupolymerization of the urea and urea ammonia with the liquid fertilizeradditives that comprise:

-   -   1) a NAPAOL,    -   2) aldehydes    -   3) one or more nitrification inhibitors selected from the group        consisting of 2-chloro-6-trichloromethyl)pyridine,        4-amino-1,2,4-6-triazole-HCl,        2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide        (DCD), thiourea, 1-mercapto-1,2,4-triazole, ammonium        thiosulfate, dimethylpyrazole and/or its organic and inorganic        salts and 2-amino-4-chloro-6-methylpyrimidine,    -   4) one or more dicyandiamide-formaldehyde adducts selected from        the group consisting of the following structures:

wherein the NAPAOL comprises one or more members selected from the groupconsisting of :

-   -   a) dimethyl sulfoxide,    -   b) and dialkyl, diaryl, or alkylaryl sulfoxide(s) having the        formula:

R₉S(O)_(x)R₁₀,

-   -   wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylene group,        an aryl group, or C₁₋₃alkylenearyl group or R₉ and R₁₀ together        with the sulfur to which they are attached form a 4 to 8        membered ring wherein R₉ and R₁₀ together are a C₁₋₆ alkylene        group which optionally contains one or more atoms selected from        the group consisting of O, S, Se, Te, N, and P in the ring and x        is 1 or 2,    -   c) and one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate d) 1-Methyl-2-pyrrolidone, e) one or more        organo phosphorous liquids selected from the group consisting of        hexamethylphosphoramide and one or more trialkylphosphates        selected from the group represented by the formula:

-   -   wherein:        -   R₂₂ is alkyl radical —C₁H₃ to —C₆H₁₃        -   R₂₃ is alkyl radical —C₁H₃ to —C₆H₁₃    -   R₂₄ is alkyl radical —C₁H₃ to —C₆H₁₃    -   f) 1,2-dimethyloxyethane, g) 2-methoxyethyl ether and h)        cyclohexylpyrrolidone, wherein the one or more aldehydes are        selected from the group consisting of:        -   methanal, ethanal, propanal, butanal, pentanal, hexanal,            methylethanal, methylpropanal, methylbutanal,            phenylacetaldehyde, benzaldehyde, 2-propenal,            3-oxopropanoic, 2-methyl-3-oxopropanoic acid, 4-oxobutanoic            acid, oxoacetic acid, 5-oxopentanoic acid, 6-oxohexanoic            acid, 2-oxopropanal, cyclohexanal, furfural, methyl esters            of 3-oxopropanoic, 2-methyl-3-oxopropanoic acid,            4-oxobutanoic acid, oxoacetic acid, 5-oxopentanoic acid and            6-oxohexanoic acid, ethandial, 1,3-propanedial, butanedial,            pentanedial, phthalaldehyde and methanethial,            wherein the said liquid fertilizer composition can added to            molten urea and/or ammonia resulting in an insitu            modification of urea and/or ammonia within the urea            manufacturing process,

and wherein the NAPAOL would have urea solubilizing properties ensuringa more homogeneous distribution of nitrification inhibitors within theurea.

have one or more properties selected from the group consisting of

-   -   higher crush resistance    -   lower water solubility due to the formation of zones of water        resistance    -   nitrification inhibition    -   extended available of nitrogen in a plant available form    -   reduced migration of nitrification inhibitor through the soil

In a variation, the resulting polymers formed have through the in situpolymerization method of making have better distribution of DCD withinthe polymer/oligomer structure ensuring lower levels of free DCD withinthe fertilizer nitrogen source particles and extending the availabilityof the nitrogen from the fertilizer in a plant available form.

In another variation, because of the slower release of the nitrificationinhibitors into the soil due to poorer water solubility and to the timefor biodegradation of the nitrification inhibitor-formaldehyde adductthat has been further reacted with urea and/or urea-ammonia, increasedlevels of application of the said liquid fertilizer additive can beadded with improved benefits from additional nitrification inhibition.

In an embodiment, a composition of a fertilizer additive ofbiodegradable polymeric and/or oligomeric nitrification inhibitors iscomprised of DCD and one or more members selected from the groupconsisting of:

-   -   a) Modified DCD represented by the structure

-   -   wherein R₄₃, R₄₄, R₄₅ and R₄₆ are one or more members        independently selected from the group consisting of: H and        —CH₂OH    -   b) a methylene bis dicyandiamide represented by the structure:

-   -   wherein R₄₇, R₄₈, R₄₉ R₅₀, R₅₁ and R₅₂ are one or more members        independently selected from the group consisting of: H, and        —CH₂OH    -   c) a trimer of a dicyandiamide-formaldehyde reaction product        represented by the structure:

-   -   wherein R₅₃, R₅₄, R₅₅ , R₅₆, R₅₇, R₅₈, R₅₉ and R₆₀ are one or        more members independently selected from the group consisting        of: H and —CH₂OH    -   d) and a polymer of a dicyandiamide-formaldehyde reaction        product represented by the structure:

-   -   wherein R₆₁, R₆₂, R₆₃, R₆₄, R₆₅, R₆₆, R₆₇ and R₆₈ are one or        more members independently selected from the group consisting        of: H and —CH₂OH    -   e) Formaldehyde

In a variation, it is recognized that generic dicyandiamide structure asdescribed herein also has tautomer shown below:

-   -   and therefore both are included in structural description.

In an embodiment, the compositions and methods of making nitrificationinhibitors are comprised of DCD and one or more members selected fromthe group consisting of:

-   -   f) Modified DCD represented by the structure

-   -   wherein R₄₃, R₄₄, R₄₅ and R₄₆ are one or more members        independently selected from the group consisting of: H and        —CH₂OH    -   g) a methylene bis dicyandiamide represented by the structure:

-   -   wherein R₄₇, R₄₈, R₄₉ R₅₀, R₅₁ and R₅₂ are one or more members        independently selected from the group consisting of: H, and        —CH₂OH    -   h) a trimer of a dicyandiamide-formaldehyde reaction product        represented by the structure:

-   -   wherein R₅₃, R₅₄, R₅₅, R₅₆, R₅₇, R₅₈, R₅₉ and R₆₀ are one or        more members independently selected from the group consisting        of: H and —CH₂OH    -   i) and a polymer of a dicyandiamide-formaldehyde reaction        product represented by the structure:

-   -   wherein R₆₁, R₆₂, R₆₃, R₆₄, R₆₅, R₆₆, R₆₇ and R₆₈ are one or        more members independently selected from the group consisting        of: H and —CH₂OH and wherein x=2-20    -   j) Formaldehyde.

The compositions and methods of the instant invention are comprised ofa) utilizing one or more non-aqueous polar, aprotic organo liquid(NAPAOL) selected from the group consisting of:

-   -   a) dimethyl sulfoxide,    -   b) an dialkyl, diaryl, or alkylaryl sulfoxide(s) having the        formula:

R₉S(O)_(x)R₁₀,

-   -   wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylene group,        an aryl group, or C₁₋₃alkylenearyl group or R₉ and R₁₀ together        with the sulfur to which they are attached form a 4 to 8        membered ring wherein R₉ and R₁₀ together are a C₁₋₆ alkylene        group which optionally contains one or more atoms selected from        the group consisting of O, S, Se, Te, N, and P in the ring and x        is 1 or 2,    -   c) one or more alkylene carbonates selected from the group        consisting of ethylene carbonate, propylene carbonate and        butylene carbonate d) 1-Methyl-2-pyrrolidone, e) one or more        organo phosphorous liquids selected from the group consisting of        hexamethylphosphoramide and one or more trialkylphosphates        selected from the group represented by the formula:

-   -   -   wherein:        -   R₂₂ is alkyl radical —C₁H₃ to —C₆H₁₃        -   R₂₃ is alkyl radical —C₁H₃ to —C₆H₁₃        -   R₂₄ is alkyl radical —C₁H₃ to —C₆H₁₃

    -   f) 1,2-dimethyloxyethane, g) 2-methoxyethyl ether and h)        cyclohexylpyrrolidone,        as the reaction medium for the reaction of formaldehyde with        dicyandiamide wherein said nitrification inhibitor composition        is applied to the soil directly either before or after the        application of a nitrogen source or in a composition with a        nitrogen source to inhibit the loss of the nitrogen source's        nitrogen caused by the microbial process termed nitrification.        In a variation, the method of making said nitrification        inhibitor compositions wherein the process parameters are        optimized to conserve the cyano group of the nitrification        inhibitor preventing it from being converted to diaminomethylene        urea comprise a) controlling pH of the reaction, b) utilization        of a NAPAOL as the reaction medium, c) using a two-step reaction        strategy wherein the first reaction incorporates formaldehyde        with dicyandiamide forming a methylol group and the second is        the reaction of the methylol group with an aldehyde reactive        group dicyandiamide to form polymeric and/or oligomeric        nitrification inhibitor composition and d) removing water during        the second reaction resulting in improved nitrification        inhibition properties.

In an embodiment, a fertilizer comprises one or more nitrogen sourcesselected from the group consisting of a) urea, b) urea formaldehydereaction products, c) ammonia, d) urea formaldehyde and ammonia reactionproducts, e) ammonium nitrate, f) ammonium sulfate, e) manure and f)compost liquid, and a nitrification inhibitor composition is comprisedof DCD and one or more nitrification inhibitors selected from the groupconsisting of :

-   -   a) Modified DCD represented by the structure

-   -   wherein R₄₃, R₄₄, R₄₅ and R₄₆ are one or more members        independently selected from the group consisting of: H and        —CH₂OH    -   b) a methylene bis dicyandiamide represented by the structure:

-   -   wherein R₄₇, R₄₈, R₄₉ R₅₀, R₅₁ and R₅₂ are one or more members        independently selected from the group consisting of: H, and        —CH₂OH    -   c) a trimer of a dicyandiamide-formaldehyde reaction product        represented by the structure:

-   -   wherein R₅₃, R₅₄, R₅₅, R₅₆, R₅₇, R₅₈, R₅₉ and R₆₀ are one or        more members independently selected from the group consisting        of: H and —CH₂OH    -   d) and a polymer of a dicyandiamide-formaldehyde reaction        product represented by the structure:

-   -   wherein R₆₁, R₆₂, R₆₃ , R₆₄, R₆₅, R₆₆, R₆₇ and R₆₈ are one or        more members independently selected from the group consisting        of: H and —CH₂OH and x=2-20,    -   e) Formaldehyde.

In a variation, said nitrification inhibitor composition can be appliedto a nitrogen source through a coating or spraying application, added tothe urea during the urea production process either in the melt portionor deposited to the urea during the formation of the urea granule whenthe urea is still hot, blended into liquefied ammonia gas and added toan aqueous fertilizers such as UAN. In a variation, application levelsof said nitrification inhibitors comprise 0.05-10% of the nitrogensource composition. In another variation, the NAPAOL comprises 0.01-9.5%of the fertilizer composition.

In an embodiment, when a nitrification inhibitor containing methylolgroups is added to a molten urea, the methylol groups can further reactwith urea, chemically incorporating the nitrification inhibitorscomposition into the urea granule. In a variation, the urea particlewill have better physical properties, more hydrophobic and contain slowrelease nitrification inhibitors in combination with more traditionalinhibitors. In a variation, the nitrification inhibitor compositions canbe added to molten urea and/or to the surface of the resulting hot ureaparticle aiding in slowing down the dissolution of the urea particle.

In an embodiment, a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors comprises utilizinga NAPAOL as the reaction medium for the reaction of aldehyde(s) withcyano-containing nitrification inhibitors and/or non-cyano-containingnitrification inhibitors that have one or more aldehyde reactive groupsselected from the group consisting of a) primary amines, b) secondaryamines, c) amides, d) thiols, e) hydroxyls and f) phenols. In avariation, said liquid fertilizer additive composition may furthercomprise one or more organo polycarboxylic acids (OPCA) and/or theirsalts. In a variation, the composition of the polyacid comprises one ormore members selected from the group consisting of a monomerhomopolymer, a copolymer and/or a terpolymer of one or more membersselected from a group consisting of :

-   -   aspartic acid    -   glutamic acid    -   maleic anhydride    -   itaconic anhydride    -   citraconic anhydride    -   citric acid; or    -   acrylic acid;

In another variation, the OPCAs are further comprised of one or moreamino polycarboxylic acids and/or their salts selected from the groupconsisting of: ethylenediaminetetraacetic acid,N-hydroxyethylethlyenediaminetriacetic acid,diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,propylenediaminetetraacetic acid, Iminodisuccinic acid,ethylenediamine-N,N′-disuccinic acid, Methylglycinediacetic acid,L-glutamic acid N,N-diacetic acid, nitrilotriacetic acid,N,Nbis(carboxymethyl)glutamic acid,Ethylenediamine-N,N′-bis(2-hydroxyphenylacetic acid,N,N′-Bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid, Glycine,N,N-ethylenebis(N-salicyl) and Iminodisuccinic acid.

wherein the organo polycarboxylic acids are present in an amount that isabout 1-50% of the total composition. In a variation, the cation of thesalts of the polyacids comprise one or more members selected from thegroup consisting of Na, K, Mg, Ca, Fe, Zn, Mn, Cu, Co, Mo, or Ni and oneor more organoamine selected from the group consisting of mono C₁₋₆amine, di C₁₋₆ amine, tri C₁₋₆ amine, mono ethanol amine, diethanolamine, triethanol amine, monoisopropyl amine, diisopropyl amine,triisopropyl amine, diethyl amine, diethylene triamine, triethyltetraamine, tetraethyl pentamine.

In an embodiment, a composition of a) liquid fertilizer additives ofbiodegradable polymeric and/or oligomeric nitrification inhibitorscomprised utilizing a NAPAOL as the reaction medium for the reaction ofaldehyde(s) with cyano-containing nitrification inhibitors and/ornon-cyano-containing nitrification inhibitors that have one or morealdehyde reactive groups selected from the group consisting of a)primary amines, b) secondary amines, c) amides, d) thiols, e) hydroxylsand f) phenols and b) one or more said organo polycarboxylic acids(OPCA) and/or their salts further comprise one or more nitrogen sourcesselected from the group consisting of: a) urea, b) urea formaldehydereaction products, c) ammonia, d) urea formaldehyde and ammonia reactionproducts, e) ammonium nitrate, f) ammonium sulfate, e) manure and f)compost. In a variation, the liquid fertilizer additives can delivernitrification inhibition and provide micro-nutrients, properties offreeing soil bound phosphates and micro-nutrients and soil conditioningproperties.

In an embodiment, a composition comprising of said biodegradablepolymeric and/or oligomeric nitrification inhibitors, OPCAs andanhydrous ammonia can deliver slow release nitrification inhibition,slow migration of nitrification inhibitors and freed/complexedphosphates and nutrients through the soil and provide soil conditioningand improved transport of moisture and nutrients in the root zonethrough sub-soil injection.

In an embodiment, a composition comprising of said biodegradablepolymeric and/or oligomeric nitrification inhibitors, OPCAs and moltenurea can deliver the benefits of the OPACs internally to urea solidparticles such as prill and granules.

In an embodiment, a composition comprising of said biodegradablepolymeric and/or oligomeric nitrification inhibitors, OPCAs in acid,ester or imide form, (aminomethyl)phosphinic acids and their salts,aminomethyl (alkylaminomethyl)phosphinic acids and their salts,dialkylaminomethyl phosphinic acids and their salts and a nitrogensource such as urea or manure can slow the loss of the nitrogen sources'ammonia, slow the conversion of ammonia to nitrates, slow the migrationof nutrients through the soil and maintain the residual phosphates andmicronutrients in a plant available form.

In an embodiment, a liquid fertilizer additive of biodegradablepolymeric and/or oligomeric nitrification inhibitors comprises utilizinga NAPAOL as the reaction medium for the reaction of aldehyde(s) withcyano-containing nitrification inhibitors and/or non-cyano-containingnitrification inhibitors that have one or more aldehyde reactive groupsselected from the group consisting of a) primary amines, b) secondaryamines, c) amides, d) thiols, e) hydroxyls and f) phenols. In avariation, said liquid fertilizer additive composition may furthercomprise one or more organo polycarboxylic acids (OPCA) and/or theirsalts selected from the group consisting of a) organo polycarboxylicacid polymers and/or their salts wherein the polymer is a monomerhomopolymer, a copolymer and/or a terpolymer comprised of one or moremembers selected from the group consisting of:

-   -   aspartic acid,    -   glutamic acid,    -   maleic anhydride,    -   itaconic anhydride,    -   citraconic anhydride,    -   citric acid, and    -   acrylic acid

b) one or more amino polycarboxylic acids and/or their salts selectedfrom the group consisting of: ethylenediaminetetraacetic acid,N-hydroxyethylethlyenediaminetriacetic acid,diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,propylenediaminetetraacetic acid, Iminodisuccinic acid,ethylenediamine-N,N′-disuccinic acid, Methylglycinediacetic acid,L-glutamic acid N,N-diacetic acid, nitrilotriacetic acid,N,Nbis(carboxymethyl)glutamic acid,Ethylenediamine-N,N′-bis(2-hydroxyphenylacetic acid,N,N′-Bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid, Glycine,N,N′-ethylenebis(N-salicyl) and Iminodisuccinic acid.

wherein the organo polycarboxylic acids are present in an amount that isabout 1-50% of a total composition and wherein a cation of salts of thepolyacids comprise one or more member selected from the group consistingof one or more metals and one or more organoamines wherein the one ormore metals are selected from the group consisting of Na, K, Mg, Ca, Fe,Zn, Mn, Cu, Co, Mo, and Ni and wherein the one or more organoamines areselected from the group consisting of mono C₁₋₆ amine, di C₁₋₆ amine,tri C₁₋₆ amine, mono ethanol amine, diethanol amine, triethanol amine,monoisopropyl amine, diisopropyl amine, triisopropyl amine, and diethylamine.

The following references are incorporated by reference in theirentireties for all purposes.

3,264,089 Hansen 3,342,577 Blauin 3,475,154 Kato 5,219,465 Goertz5,538,531 Hudson 5,599,374 Detrick 5,653,782 Stern 5,803,946 Petcavich6,338,746 Detrick 6,663,686 Geiger 9,440,890 Gabrielson 20100011825 Ogle20040016276 Wynnyk CN104803807 Yuan CN104446875 Li CN104609983 Chen4,551,166 Behnke

Baligar V C, B. O. (1986). “NPK-fertilizer efficiency—a situationanalysis for the tropics.” Fertilizer Research 10(2): 147-164.

Bennett E M, C. S. a. C. N. (2001). “Human Impact on Erodable Phosphorusand Eutrophication: A Global Perspective

Increasing accumulation of phosphorus in soil threatens rivers, lakes,and coastal oceans with eutrophication.” BioScience 51: 227-234.

Christians, N. (2004). ““Fertilization”. Fundamentals of TurfgrassManagement (2nd ed.).” 137-138.

Dobermann, A. and K. G. Cassman (2005). “Cereal area and nitrogen useefficiency are drivers of future nitrogen fertilizer consumption.” SciChina C Life Sci 48 Spec No: 745-758.

Fan, X., Li, F., Liu, F., and Kumar, D. (2004). “Fertilization with anew type of coated urea: Evaluation for nitrogen efficiency and yield inwinter wheat.” J. Plant Nutr. 27: 853-865.

Kross, B. C., et al. (1993). “The nitrate contamination of private wellwater in Iowa.” Am J Public Health 83(2): 270-272.

TLAL (1998). “Soil quality and agricultural sustainability.” 58.

Linsay, W. (1979). “Chemical Equilibrium in Soils.”

S, S. (2012). “An Agricultural Pollutant: Chemical Fertilizer.”International Journal of Environmental Science and Development 3(1): 77.

Ebisuno, Takimoto, Takahashi, Shiba, (1993) “Preparation and Structureof a Tetrasubstituted Derivative of N″-Cyanoguanidine,N,N,N′,N′-Tetrabenzyl-N″-cyanoguanidine.”

It should be understood that the present invention is not to be limitedby the above description. Modifications can be made to the above withoutdeparting from the spirit and scope of the invention. It is contemplatedand therefore within the scope of the present invention that any featurethat is described above can be combined with any other feature that isdescribed above. Moreover, it should be understood that the presentinvention contemplates minor modifications that can be made to theformulations, compositions, fertilizer additives and methods of thepresent invention. When ranges are discussed, any number that may not beexplicitly disclosed but fits within the range is contemplated as anendpoint for the range. For example, if a range of 35-60 is given, itshould be understood, that any number between 35 and 60 can be used asthe end point for said range (e.g., 36, 37, 38, etc.). Moreover, if alist of species within a genus are listed, it is contemplated that anyparticular species or any group of species within the genus iscontemplated as being a subgenus that fits within the scope of theinvention. The scope of protection to be afforded is to be determined bythe claims which follow and the breadth of interpretation which the lawallows.

We claim: 1) A liquid fertilizer additive composition comprising a) anon-aqueous polar, aprotic organic liquid (NAPAOL) and b) anitrification inhibitor composition wherein the NAPAOL comprises one ormore members selected from the group consisting of: i) dimethylsulfoxide, ii) dialkyl, diaryl, or alkylaryl sulfoxide(s) having theformula:R₉S(O)_(x)R₁₀ wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylenegroup, an aryl group, or C₁₋₃alkylenearyl group or R₉ and R₁₀ togetherwith the sulfur to which they are attached form a 4 to 8 membered ringwherein R₉ and R₁₀ together are a C₁₆ alkylene group which optionallycontains one or more atoms selected from the group consisting of O, S,Se, Te, N, and P in the ring and x is 1 or 2, iii) one or more alkylenecarbonates selected from the group consisting of ethylene carbonate,propylene carbonate and butylene carbonate iv) 1-Methyl-2-pyrrolidone,v) one or more organo phosphorous liquids selected from the groupconsisting of hexamethylphosphoramide and one or more trialkylphosphatesselected from the structure:

wherein: R₂₂ is an alkyl radical —C₁H₃ to —C₆H₁₃ R₂₃ is an alkyl radical—C₁H₃ to —C₆H₁₃ R₂₄ is an alkyl radical —C₁H₃ to —C₆H₁₃ vi)1,2-dimethyloxyethane, vii) 2-methoxyethyl ether, and viii)cyclohexylpyrrolidone, and wherein the nitrification compositioncomprises one or more members selected from the structures consistingof:

wherein R₄₃, R₄₄, R₄₅ and R₄₆ are one or more members independentlyselected from the group consisting of: H and —CH₂OH wherein at least oneof R₄₃, R₄₄, R₄₅ and R₄₆ is —CH₂OH,

wherein R₄₇, R₄₈, R₄₉ R₅₀, R₅₁ and R₅₂ are one or more membersindependently selected from the group consisting of: H, and —CH₂OH, and

wherein R₅₃, R₅₄, R₅₅ , R₅₆, R₅₇, R₅₈, R₅₉ and R₆₀ are one or moremembers independently selected from the group consisting of: H and—CH₂OH. 2) The composition of claim 1 wherein the composition furthercomprises one or more compounds from the structure:

wherein R₆₁, R₆₂, R₆₃, R₆₄, R₆₅, R₆₆, R₆₇ and R₆₈ are one or moremembers independently selected from the group consisting of: H and—CH₂OH and x is 2-20. 3) The composition of claim 1 wherein thecomposition further comprises one or more members selected from thegroup consisting of triazone, paraformaldehyde, dicyandiamide (DCD) andformaldehyde. 4) The composition of claim 1, wherein the nitrificationinhibitor composition further comprises one or more members selectedfrom the group consisting of a) ammonia, b) polyamines, c) polyols, d)primary amines, e) secondary amines, f) low molecular weight alcohols,and g) non-cyano containing nitrification inhibitors wherein one or morepolyamines are selected from the group consisting of ethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine andaminoethylethanolamine, and wherein the polyamines comprise 0.01-5% of anitrification inhibitor weight, wherein one or more polyols are selectedfrom the group consisting of trimethylol propane, trimethylol ethane,pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose,glycerin, poly(C₁₋₁₀ alkylene) glycols, ethylene, 1,3 propylene glycol,1,2 propylene glycol, butylene glycol, isopropylidene glycerol,tripropylene glycol methyl ether, tripropylene glycol butyl ether,dipropylene glycol butyl ether, and tripropylene glycol butyl etherwherein the polyols comprise 0.1-5% of the nitrification inhibitorweight, wherein one or more secondary amines are selected from the groupconsisting of diethanolamine, diethylamine, cyclohexylamine,methylethanolamine, diisopropanolamine, methylispropylamine wherein thesecondary amines comprise 0.1-5% of the nitrification inhibitor weight,wherein one or more low molecular weight alcohols are selected from thegroup consisting of methanol, ethanol, butanol, pentanol, and hexanolwherein the low molecular weight alcohols comprise 0.1-5% of thenitrification inhibitor weight, wherein one or more non-cyano containingnitrification inhibitors are selected from the group consisting of: i)one or more pyrazoles represented by the structure:

wherein R₂₈=—H, —CH₃, —CH₂CH₃, —NH₂ or —NHCH₃, wherein R₂₉=—H, —OH, —SH,—CONH₂ or —CONHCH₃, wherein R₃₀=—H, —CH₃, —CH₂CH₃, —NH₂ or —NHCH₃, andwherein R₃₁=—H, —CH₃, —CH₂CH₃, —NH₂ or —NHCH₃, ii) one or more membersselected from the group consisting of2-amino-4-chloro-6-methyl-pyrimidine, 1,3-benzothiazole-2-thiol,4-amino-N-1,3-thiazol-2-ylbenzenesulfonamide, thiourea,2,4-diamino-6-trichloromethyl-5-triazine, 4-amino-1,2,4-triazole,3-mercapto-1,2,4-triazole, and 2,3-dihydro-2,2-dimethyl-7-benzofuranolmethyl-carbamate. 5) The composition of claim 1, wherein the compositionfurther comprises one or more members selected from the group consistingof: a) surfactants, buffers, fragrance/odor masking agents, colorants,flow modifiers, silicas, and hydrophobized silicas, b) one or morenon-aqueous organo liquids selected from the group consisting of polaraprotic, aprotic, and protic organo solvents wherein: one or moreaprotic solvents are selected from the group consisting of: i) one ormore polyols capped with acetate or formate wherein a polyol portion isselected from the group consisting of ethylene glycol, 1,3 propyleneglycol, 1,2 propylene glycol, butylene glycol, trimethylol propane,trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose,fructose, galactose and glycerin, ii) one or more alkylene glycol alkylether acetates are selected from the group consisting of dipropyleneglycol methyl ether acetate, tripropylene glycol methyl ether acetate,and tripropylene glycol butyl ether acetate, iii) isophorone, iv) one ormore diesters are selected from the group consisting ofdimethylsuccinate, dimethyl adipate, diethyl glutarate, and dimethylglutarate, v) dimethylacetamide, vi) dimethylformamide, vii)dimethyl-2-imidazolidinone, viii) 1-Methyl-2-pyrrolidone and ix)limonene, wherein one or more protic solvents are selected from thegroup consisting of: i) an alcohol from the family of C₁₋₁₀ alkanols,ii) one or more polyols are selected from the group consisting oftrimethylol propane, trimethylol ethane, pentaerythritol, sorbitol,sorbitan, glucose, fructose, galactose, and glycerin, iii) one or morepoly(C₁₋₁₀ alkylene) glycols represented by the structure:H(C_(t)H_(u))_(v)OH, wherein t is an integer: 1-10 u is an integer: 2-20and v is an integer: 1-20, iv) one or more alkylene glycols are selectedfrom the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2propylene glycol, and butylene glycol, v) isopropylidene glycerol vi)one or more alkylene glycol alkyl ethers are selected from the grouprepresented by the structure:

wherein R¹ is: CH₃, C₂H₅, C₃H₇ or C₄H₉ wherein R² is: H or the structure

wherein R³ is: H or CH₃ wherein R⁴ is H or CH₃ and f is an integerbetween 1 and 15, vii) one or more alkyl lactates are selected from thegroup consisting of ethyl, propyl and butyl lactate, viii) one or morealkanolamines are selected from the group represented by the structure:

wherein R⁵ is: C₂H₄OR⁸ or C₃H₆OH wherein R⁶ is: H, C₂H₄OR⁸ or C₃H₆OHwherein R⁷ is: H, C₂H₄OR⁸ or C₃H₆OH wherein R⁸ is: (C₂H₄O)_(g)H and g isan integer between 1-10 and ix) glycerol carbonate, wherein one or morepolar aprotic solvents are selected from the group consisting of: i)dimethyl sulfoxide, ii) dialkyl, diaryl, or alkylaryl sulfoxide(s)having the formula:R₉S(O)_(x)R₁₀ wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylenegroup, an aryl group, or C₁₋₃alkylenearyl group, or R₉ and R₁₀ togetherwith the sulfur to which they are attached form a 4 to 8 membered ringwherein R₉ and R₁₀ together are a C₁₋₆ alkylene group which optionallycontains one or more atoms selected from the group consisting of O, S,Se, Te, N, and P in the ring and x is 1 or 2, and optionally furthercomprising iii) one or more alkylene carbonates are selected from thegroup consisting of ethylene carbonate, propylene carbonate and butylenecarbonate iv) 1-Methyl-2-pyrrolidone, v) one or more organo phosphorousliquids are selected from the group consisting ofhexamethylphosphoramide and one or more trialkylphosphates are selectedfrom the group represented by the structure:

wherein: R₂₂ is an alkyl radical —C₁H₃ to —C₆H₁₃ R₂₃ is an alkyl radical—C₁H₃ to —C₆H₁₃ R₂₄ is an alkyl radical —C₁H₃ to —C₆H₁₃ vi)1,2-dimethyloxyethane, vii) 2-methoxyethyl ether and vii)cyclohexylpyrrolidone. 6) The composition of claim 1, wherein thecomposition further comprises one or more members selected from thegroup consisting of: a) one or more biologics selected from the groupconsisting of: i) Bacillus biologics, ii) Azospirillum biologics, iii)Azobacter biologics iv) Gluconacetobacter biologics, v) Phosphobacteria,vi) Cyanobacteria, vii) Herbaspirillum, viii) Burkholderia, ix)Pseudomonas, x) Gluconacetobacter, xi) Enterobacter, xii) Klebsiella,xiii) Burkholderia, xiv) Bradyrhiwbium species, xv) Bradyrhiwbiumjaponicum, xvi) Rhizobium meliloti, xvii) Laccaria bicolor, xviii)Glomus imraradices timanita, xix) Actinomyces, xx) Penicillium, xxi)Mesorhizobiwn cicero, xxii) one or more insecticidal or insect repellentmicrobial species and strains are selected from the group consisting of:Telenomus podisi, Baculovirus anticarsia; Trichogramma pretiosum,Trichogramma gallai, Chromobacterium subtsugae, Trichoderma fertile,Beauveria bassiana, Beauveria bassiana, Beauveria bassiana, Paecilomycesjknwsoroseu, Trichoderma harzianum, Verticillium lecanii,lswfofumosarosea Lecanicillium muscarium, Streptomyces microflavus, andMuscodor albus, xxiii) one or more nematodal microbial species andstrains are selected from the group consisting of: Myrotheciumverrucaria, Pasteuria species, Pasteuria Metarhizium species, andFlavobacteriwn species xxiv) Reynoutria sachalinensis and xxv) one ormore antifungal, antimicrobial and/or plant growth promoting microbialspecies and strains are selected from the group consisting ofGliocladium species, Pseudomonas species selected from the groupconsisting of: Pseudomonas fluorescens, Pseudomonas fluorescens. putidaand P. chlororaphis, Pseudomonasfluorescens VP5, Pseudomonasdiazotrophicus, Enterobacter cloacae, Trichodema species, Trichodermavirens, Trichoderma atroviride strains, Coniothyrium minitans,Gliocladium species, Gliacladium virens, Gliacladium roseum, andTrichodemw harzianum species, b) and one or more biologically activeagents are selected from the group consisting of: i) one or more ureaseinhibitors are selected from the group consisting of aliphaticphosphoric triamide, phosphoramides, N-alkyl thiophosphoric triamides,(aminomethyl)phosphinic acids and their salts and aminomethyl(alkylaminomethyl)phosphinic acids and their salts, ii) one or morenitrification inhibitors are selected from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4,6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD),thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate,dimethylpyrazole organic and inorganic salts, and2-amino-4-chloro-6-methylpyrimidine, iii) and one or more membersselected from the group consisting of pesticide(s), herbicidesfungicides(s), and insecticide(s). 7) The composition of claim 1,wherein the composition further comprises one or more organopolycarboxylic acids selected from the group consisting of a) organopolycarboxylic acid polymers and/or their salts wherein the polymer is ahomopolymer, a copolymer and/or a terpolymer comprised of one or moremembers selected from the group consisting of: aspartic acid, glutamicacid, maleic anhydride, itaconic anhydride, citraconic anhydride, citricacid, and acrylic acid b) one or more amino polycarboxylic acids and/ortheir salts selected from the group consisting of:ethylenediaminetetraacetic acid, N-hydroxyethylethlyenediaminetriaceticacid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraaceticacid, propylenediaminetetraacetic acid, Iminodisuccinic acid,ethylenediamine-N,N′-disuccinic acid, Methylglycinediacetic acid,L-glutamic acid N,N-diacetic acid, nitrilotriacetic acid,N,Nbis(carboxymethyl)glutamic acid,Ethylenediamine-N,N′-bis(2-hydroxyphenylacetic acid,N,N′-Bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid, Glycine,N,N′-ethylenebis(N-salicyl) and Iminodisuccinic acid. wherein the organopolycarboxylic acids are present in an amount that is about 1-50% of atotal composition and wherein a cation of salts of the polyacidscomprise one or more member selected from the group consisting of one ormore metals and one or more organoamines wherein the one or more metalsare selected from the group consisting of Na, K, Mg, Ca, Fe, Zn, Mn, Cu,Co, Mo, and Ni and wherein the one or more organoamines are selectedfrom the group consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri C₁₋₆amine, mono ethanol amine, diethanol amine, triethanol amine,monoisopropyl amine, diisopropyl amine, triisopropyl amine, and diethylamine. 8) A fertilizer composition comprised of: a) one or more nitrogensources selected from the group consisting of: i) urea, ii) ureaformaldehyde reaction products, iii) ammonia, iv) urea formaldehyde andammonia reaction products, v) ammonium nitrate, vi) ammonium sulfate,vii) manure viii) compost and ix) treated urea and b) A liquidfertilizer additive composition comprising i) a non-aqueous polar,aprotic organic liquid (NAPAOL) and ii) a nitrification inhibitorcomposition wherein NAPAOL comprises one or more members selected fromthe group consisting of: (1) dimethyl sulfoxide, (2) dialkyl, diaryl, oralkylaryl sulfoxide(s) having the formula:R₉S(O)_(x)R₁₀ wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylenegroup, an aryl group, or C₁₋₃alkylenearyl group or R₉ and R₁₀ togetherwith the sulfur to which they are attached form a 4 to 8 membered ringwherein R₉ and R₁₀ together are a C₁₆ alkylene group which optionallycontains one or more atoms selected from the group consisting of O, S,Se, Te, N, and P in the ring and x is 1 or 2, (3) one or more alkylenecarbonates selected from the group consisting of ethylene carbonate,propylene carbonate and butylene carbonate (4) 1-Methyl-2-pyrrolidone,(5) one or more organo phosphorous liquids selected from the groupconsisting of hexamethylphosphoramide and one or more trialkylphosphatesselected from the structure:

wherein: R₂₂ is an alkyl radical —C₁H₃ to —C₆H₁₃ R₂₃ is an alkyl radical—C₁H₃ to —C₆H₁₃ R₂₄ is an alkyl radical —C₁H₃ to —C₆H₁₃ (6)1,2-dimethyloxyethane, (7) 2-methoxyethyl ether, and (8)cyclohexylpyrrolidone, and wherein the nitrification compositioncomprises one or more members selected from the structures consistingof:

wherein R₄₃, R₄₄, R₄₅ and R₄₆ are one or more members independentlyselected from the group consisting of: H and —CH₂OH wherein at least oneof R₄₃, R₄₄, R₄₅ and R₄₆ is —CH₂OH,

wherein R₄₇, R₄₈, R₄₉ R₅₀, R₅₁ and R₅₂ are one or more membersindependently selected from the group consisting of: H, and —CH₂OH,

wherein R₅₃, R₅₄, R₅₅, R₅₆, R₅₇, R₅₈, R₅₉ and R₆₀ are one or moremembers independently selected from the group consisting of: H and—CH₂OH. 9) The composition of claim 8 wherein the nitrificationinhibitor composition further comprises the structure:

wherein R₆₁, R₆₂, R₆₃, R₆₄, R₆₅, R₆₆, R₆₇ and R₆₈ are one or moremembers independently selected from the group consisting of: H and—CH₂OH and wherein x is 2-20. 10) The composition of claim 8 whereincomposition further comprises one or more members selected from thegroup consisting of triazone, paraformaldehyde, DCD and formaldehyde.11) The composition of claim 8, wherein the nitrification inhibitorcomposition further comprises one or more members selected from thegroup consisting of a) ammonia, b) polyamines, c) polyols, d) primaryamines, e) secondary amines, f) low molecular weight alcohols, and g)non-cyano containing nitrification inhibitors, wherein one or morepolyamines are selected from the group consisting of ethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine andaminoethylethanolamine, and wherein the polyamines comprise 0.01-5% of anitrification inhibitor weight, wherein one or more polyols are selectedfrom the group consisting of trimethylol propane, trimethylol ethane,pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose,glycerin, poly(C₁₋₁₀ alkylene) glycols, ethylene, 1,3 propylene glycol,1,2 propylene glycol, butylene glycol, isopropylidene glycerol,tripropylene glycol methyl ether, tripropylene glycol butyl ether,dipropylene glycol butyl ether, and tripropylene glycol butyl etherwherein the polyols comprise 0.1-5% of the nitrification inhibitorweight, wherein one or more secondary amines are selected from the groupconsisting of diethanolamine, diethylamine, cyclohexylamine,methylethanolamine, diisopropanolamine, methylispropylamine wherein thesecondary amines comprise 0.1-5% of the nitrification inhibitor weight,wherein one or more low molecular weight alcohols are selected from thegroup consisting of methanol, ethanol, butanol, pentanol, and hexanolwherein the low molecular weight alcohols comprise 0.1-5% of thenitrification inhibitor weight, wherein one or more non-cyano containingnitrification inhibitors are selected from the group consisting of: i)one or more pyrazoles represented by the structure:

wherein R₂₈=—H, —CH₃, —CH₂CH₃, —NH₂ or —NHCH₃, wherein R₂₉=—H, —OH, —SH,—CONH₂ or —CONHCH₃, wherein R₃₀=—H, —CH₃, —CH₂CH₃, —NH₂ or —NHCH₃, andwherein R₃₁=—H, —CH₃, —CH₂CH₃, —NH₂ or —NHCH₃, ii) one or more membersselected from the group consisting of2-amino-4-chloro-6-methyl-pyrimidine, 1,3-benzothiazole-2-thiol,4-amino-N-1,3-thiazol-2-ylbenzenesulfonamide, thiourea,2,4-diamino-6-trichloromethyl-5-triazine, 4-amino-1,2,4-triazole,3-mercapto-1,2,4-triazole, and 2,3-dihydro-2,2-dimethyl-7-benzofuranolmethyl-carbamate. 12) The composition of claim 1, wherein thecomposition further comprises one or more members selected from thegroup consisting of: a) surfactants, buffers, fragrance/odor maskingagents, colorants, flow modifiers, silicas, and hydrophobized silicas,b) one or more non-aqueous organo liquids selected from the groupconsisting of polar aprotic, aprotic, and protic organo solventswherein: one or more aprotic solvents are selected from the groupconsisting of: i) one or more polyols capped with acetate or formatewherein a polyol portion is selected from the group consisting ofethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, butyleneglycol, trimethylol propane, trimethylol ethane, pentaerythritol,sorbitol, sorbitan, glucose, fructose, galactose and glycerin, ii) oneor more alkylene glycol alkyl ether acetates are selected from the groupconsisting of dipropylene glycol methyl ether acetate, tripropyleneglycol methyl ether acetate, and tripropylene glycol butyl etheracetate, iii) isophorone, iv) one or more diesters are selected from thegroup consisting of dimethylsuccinate, dimethyl adipate, diethylglutarate, and dimethyl glutarate, v) dimethylacetamide, vi)dimethylformamide, vii) dimethyl-2-imidazolidinone, viii)1-Methyl-2-pyrrolidone and ix) limonene, wherein one or more proticsolvents are selected from the group consisting of: i) an alcohol fromthe family of C₁₋₁₀ alkanols, ii) one or more polyols are selected fromthe group consisting of trimethylol propane, trimethylol ethane,pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose, andglycerin, iii) one or more poly(C₁₋₁₀ alkylene) glycols represented bythe structure:H(C_(t)H_(u))_(v)OH, wherein t is an integer: 1-10 u is an integer: 2-20and v is an integer: 1-20, iv) one or more alkylene glycols are selectedfrom the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2propylene glycol, and butylene glycol, v) isopropylidene glycerol vi)one or more alkylene glycol alkyl ethers are selected from the grouprepresented by the structure:

wherein R¹ is: CH₃, C₂H₅, C₃H₇ or C₄H₉ wherein R² is: H or the structure

wherein R³ is: H or CH₃ wherein R⁴ is H or CH₃ and f is an integerbetween 1 and 15, vii) one or more alkyl lactates are selected from thegroup consisting of ethyl, propyl and butyl lactate, viii) one or morealkanolamines are selected from the group represented by the structure:

wherein R⁵ is: C₂H₄OR⁸ or C₃H₆OH wherein R⁶ is: H, C₂H₄OR⁸ or C₃H₆OHwherein R⁷ is: H, C₂H₄OR⁸ or C₃H₆OH wherein R⁸ is: (C₂H₄O)_(g)H and g isan integer between 1-10 ix) and glycerol carbonate, wherein one or morepolar aprotic solvents are selected from the group consisting of i)dimethyl sulfoxide, ii) dialkyl, diaryl, and alkylaryl sulfoxide(s)having the formula:R₉S(O)_(x)R₁₀ wherein R₉ and R₁₀ are each independently a C₁₋₆ alkylenegroup, an aryl group, or C₁₋₃alkylenearyl group, or R₉ and R₁₀ togetherwith the sulfur to which they are attached form a 4 to 8 membered ringwherein R₉ and R₁₀ together are a C₁₋₆ alkylene group which optionallycontains one or more atoms selected from the group consisting of O, S,Se, Te, N, and P in the ring and x is 1 or 2, and optionally furthercomprising iii) one or more alkylene carbonates are selected from thegroup consisting of ethylene carbonate, propylene carbonate and butylenecarbonate iv) 1-Methyl-2-pyrrolidone, v) one or more organo phosphorousliquids are selected from the group consisting ofhexamethylphosphoramide and one or more trialkylphosphates are selectedfrom the group represented by the structure:

wherein: R₂₂ is an alkyl radical —C₁H₃ to —C₆H₁₃ R₂₃ is an alkyl radical—C₁H₃ to —C₆H₁₃ R₂₄ is an alkyl radical —C₁H₃ to —C₆H₁₃ vi)1,2-dimethyloxyethane, vii) 2-methoxyethyl ether and vii)cyclohexylpyrrolidone. 13) The composition of claim 8, wherein thecomposition further comprises one or more members selected from thegroup consisting of: a) one or more biologics selected from the groupconsisting of: i) Bacillus biologics, ii) Azospirillum biologics, iii)Azobacter biologics iv) Gluconacetobacter biologics, v) Phosphobacteria,vi) Cyanobacteria, vii) Herbaspirillum, viii) Burkholderia, ix)Pseudomonas, x) Gluconacetobacter, xi) Enterobacter, xii) Klebsiella,xiii) Burkholderia, xiv) Bradyrhiwbium species, xv) Bradyrhiwbiumjaponicum, xvi) Rhizobium meliloti, xvii) Laccaria bicolor, xviii)Glomus imraradices timanita, xix) Actinomyces, xx) Penicillium, xxi)Mesorhizobiwn cicero, xxii) one or more insecticidal or insect repellentmicrobial species and strains are selected from the group consisting of:Telenomus podisi, Baculovirus anticarsia; Trichogramma pretiosum,Trichogramma gallai, Chromobacterium subtsugae, Trichoderma fertile,Beauveria bassiana, Beauveria bassiana, Beauveria bassiana, Paecilomycesjknwsoroseu, Trichoderma harzianum, Verticillium lecanii,lswfofumosarosea Lecanicillium muscarium, Streptomyces microflavus, andMuscodor albus, xxiii) one or more nematodal microbial species andstrains are selected from the group consisting of: Myrotheciumverrucaria, Pasteuria species, Pasteuria Metarhizium species, andFlavobacteriwn species xxiv) Reynoutria sachalinensis and xxv) one ormore antifungal, antimicrobial and/or plant growth promoting microbialspecies and strains are selected from the group consisting ofGliocladium species, Pseudomonas species selected from the groupconsisting of: Pseudomonas fluorescens, Pseudomonas fluorescens. putidaand P. chlororaphis, Pseudomonasfluorescens VP5, Pseudomonasdiazotrophicus, Enterobacter cloacae, Trichodema species, Trichodermavirens, Trichoderma atroviride strains, Coniothyrium minitans,Gliocladium species, Gliacladium virens, Gliacladium roseum, andTrichodemw harzianum species, b) and one or more biologically activeagents are selected from the group consisting of: i) one or more ureaseinhibitors are selected from the group consisting of aliphaticphosphoric triamide, phosphoramides, N-alkyl thiophosphoric triamides,(aminomethyl)phosphinic acids and their salts and aminomethyl(alkylaminomethyl)phosphinic acids and their salts, ii) one or morenitrification inhibitors are selected from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4,6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD),thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate,dimethylpyrazole organic and inorganic salts, and2-amino-4-chloro-6-methylpyrimidine, iii) and one or more membersselected from the group consisting of pesticide(s), herbicidesfungicides(s), and insecticide(s). 14) The composition of claim 8,wherein the composition further comprises one or more organopolycarboxylic acids selected from the group consisting of a) organopolycarboxylic acid polymers and/or their salts wherein the polymer is ahomopolymer, a copolymer and/or a terpolymer comprised of one or moremembers selected from the group consisting of: aspartic acid, glutamicacid, maleic anhydride, itaconic anhydride, citraconic anhydride, citricacid, and acrylic acid b) one or more amino polycarboxylic acids and/ortheir salts selected from the group consisting of:ethylenediaminetetraacetic acid, N-hydroxyethylethlyenediaminetriaceticacid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraaceticacid, propylenediaminetetraacetic acid, Iminodisuccinic acid,ethylenediamine-N,N′-disuccinic acid, Methylglycinediacetic acid,L-glutamic acid N,N-diacetic acid, nitrilotriacetic acid,N,Nbis(carboxymethyl)glutamic acid,Ethylenediamine-N,N′-bis(2-hydroxyphenylacetic acid,N,N-Bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid, Glycine,N,N′-ethylenebis(N-salicyl) and Iminodisuccinic acid. wherein the organopolycarboxylic acids are present in an amount that is about 1-50% of atotal composition and wherein a cation of salts of the polyacidscomprise one or more member selected from the group consisting of one ormore metals and one or more organoamines wherein the one or more metalsare selected from the group consisting of Na, K, Mg, Ca, Fe, Zn, Mn, Cu,Co, Mo, and Ni and wherein the one or more organoamines are selectedfrom the group consisting of mono C₁₋₆ amine, di C₁₋₆ amine, tri C₁₋₆amine, mono ethanol amine, diethanol amine, triethanol amine,monoisopropyl amine, diisopropyl amine, triisopropyl amine, and diethylamine. 15) The composition of claim 8 wherein treated urea is comprisedof urea and one or more members selected from the group consisting of a)urea formaldehyde polymer, b) urea formaldehyde reaction adducts, c)biologics d) biologically active agents and e) organo polycarboxylicacids and/or their salt wherein the one or more biologics are selectedfrom the group consisting of: i) Bacillus biologics, ii) Azospirillumbiologics, iii) Azobacter biologics iv) Gluconacetobacter biologics, v)Phosphobacteria, vi) Cyanobacteria, vii) Herbaspirillum, viii)Burkholderia, ix) Pseudomonas, x) Gluconacetobacter, xi) Enterobacter,xii) Klebsiella, xiii) Burkholderia, xiv) Bradyrhiwbium species, xv)Bradyrhiwbium japonicum, xvi) Rhizobium meliloti, xvii) Laccariabicolor, xviii) Glomus imraradices timanita, xix) Actinomyces, xx)Penicillium, xxi) Mesorhizobiwn cicero, xxii) one or more insecticidalor insect repellent microbial species and strains are selected from thegroup consisting of: Telenomus podisi, Baculovirus anticarsia;Trichogramma pretiosum, Trichogramma gallai, Chromobacterium subtsugae,Trichoderma fertile, Beauveria bassiana, Beauveria bassiana, Beauveriabassiana, Paecilomyces jknwsoroseu, Trichoderma harzianum, Verticilliumlecanii, lswfofumosarosea Lecanicillium muscarium, Streptomycesmicroflavus, and Muscodor albus, xxiii) one or more nematodal microbialspecies and strains are selected from the group consisting of:Myrothecium verrucaria, Pasteuria species, Pasteuria Metarhiziumspecies, and Flavobacteriwn species xxiv) Reynoutria sachalinensis andxxv) one or more antifungal, antimicrobial and/or plant growth promotingmicrobial species and strains are selected from the group consisting of:Gliocladium species, Pseudomonas species selected from the groupconsisting of: Pseudomonas fluorescens, Pseudomonas fluorescens. putidaand P. chlororaphis, Pseudomonasfluorescens VP5, Pseudomonasdiazotrophicus, Enterobacter cloacae, Trichodema species, Trichodermavirens, Trichoderma atroviride strains, Coniothyrium minitans,Gliocladium species, Gliacladium virens, Gliacladium roseum, andTrichodemw harzianum species, and wherein one or more biologicallyactive agents selected from the group consisting of: i) one or moreurease inhibitors selected from the group consisting of aliphaticphosphoric triamide, phosphoramides, N-alkyl thiophosphoric triamides,(aminomethyl)phosphinic acids and their salts and aminomethyl(alkylaminomethyl)phosphinic acids and their salts, ii) one or morenitrification inhibitors selected from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4,6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD),thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate,dimethylpyrazole organic and inorganic salts, and2-amino-4-chloro-6-methylpyrimidine, iii) and one or more membersselected from the group consisting of pesticide(s), herbicidesfungicides(s), and insecticide(s). 16) The composition of claim 8wherein the NAPAOL comprises dimethyl sulfoxide. 17) The composition ofclaim 8 wherein the composition is made using at least one of thefollowing application techniques: a) coating a nitrogen source with saidliquid fertilizer additives utilizing spraying, metering or slowlypouring onto the surface of nitrogen source, b) incorporating saidliquid fertilizer additives during the processing of a nitrogen sourcewherein the liquid fertilizer additive can be added directly into themolten nitrogen source before formation of a particle, granule and/or aprill, applied/sprayed onto the surface of a molten nitrogen sourceduring the formation of a particle, granule and/or a prill and/orsprayed onto a surface of a nitrogen source during the formation of aparticle, granule and/or a prill, c) dissolving said liquid fertilizeradditives into aqueous liquid fertilizers, or d) incorporating saidliquid fertilizer additives into one or more non-aqueous liquid nitrogensources selected from the group consisting of pressurized anhydrousammonia gas and non-pressurized anhydrous ammonia gas. 18) Thecomposition of claim 8 wherein the composition of the nitrogen sourcecomprises one or more members selected from the group consisting of ureaand ammonium nitrate. 19) The composition of claim 18, wherein thecomposition further comprises water. 20) The composition of claim 1,wherein said liquid fertilizer additive composition is applied to thesoil directly either before or after the application of a nitrogensource or in a composition with a nitrogen source to inhibit the loss ofthe nitrogen source's nitrogen caused by the microbial process ofnitrification.